Intercalates and expoliates formed with organic pesticide compounds and compositions containing the same

ABSTRACT

Intercalates formed by contacting an activated layered material, e.g., an activated phyllosilicate, with an intercalant pesticide to intercalate an intercalant pesticide between adjacent platelets of the layered material is disclosed. Sufficient intercalant pesticide is sorbed between adjacent platelets to expand the adjacent platelets to a spacing of at least about 5 Å (as measured after water removal to a maximum of 5% by weight water) up to about 100 Å, and preferably in the range of about 10 to about 45 Å, so that, if desired, the intercalate can be exfoliated into individual platelets. The intercalate can be combined with an organic liquid to form a viscous composition for delivery of a pesticide compound. Alternatively, the intercalate can be exfoliated prior to combination with the organic liquid. The intercalated complex also can be admixed with solid particles to provide a granular, dust, or wettable powder pesticide composition.

FIELD OF THE INVENTION

The present invention is directed to intercalated pesticidesmanufactured by intercalation of one or more organic pesticide compoundsbetween planar layers of a swellable layered material. Moreparticularly, the present invention is directed to intercalates havingat least one layer of organic pesticide compound sorbed on the internalsurfaces of adjacent layers of the planar platelets of a layeredmaterial, such as a phyllosilicate, preferably a smectite clay, toexpand the interlayer spacing to at least about 5 Å, preferably at leastabout 10 Å, more preferably to at least about 20 Å, and most preferablyto at least about 30 Å, up to about 100 Å, or disappearance ofperiodicity. The intercalated layered materials have at least one layerof pesticide compound sorbed on the internal surfaces between adjacentlayers of the planar platelets of the layered material. The resultingintercalates are a combination of organophilic and hydrophilic, and, ifdesired, can be exfoliated to individual platelets. The intercalates orexfoliates can be combined with an organic solvent to form a viscouspesticide composition or a thixotropic gel.

BACKGROUND OF THE INVENTION AND PRIOR ART

Calcined clays traditionally have been used as carriers for granularpesticides. Granular pesticides having a calcined clay carrier arelimited because such carriers can accommodate no more than about 10% byweight of a pesticide. The amount of pesticide is limited because thepesticide merely enters the pore structure of the calcined clay. Whenthe available sites in the pore structure are filled, then no furtherpesticide can be held by the calcined clay. If the available surfacearea of the carrier was greater, the amount of pesticide in a granularproduct could be increased up to about 30% to 40% by weight of thepesticide granule.

It also is well known that phyllosilicates, such as smectite clays,e.g., sodium montmorillonite and calcium montmorillonite, can be treatedwith organic molecules, such as organic ammonium ions, to intercalateorganic molecules between adjacent, planar silicate layers, for bondingthe organic molecules with a polymer to intercalate the polymer betweenthe layers, thereby substantially increasing the interlayer(interlaminar) spacing between the adjacent silicate layers. Thethus-treated, intercalated phyllosilicates, having interlayer spacingsof at least about 10 Å and up to about 100 Å, then can be exfoliated,i.e., the silicate layers are separated, e.g., mechanically, by highshear mixing. The individual silicate layers, when admixed with a matrixpolymer, before, after or during the polymerization of the matrixpolymer, e.g., a polyamide--see U.S. Pat. Nos. 4,739,007; 4,810,734; and5,385,776--have been found to substantially improve one or moreproperties of the polymer, such as mechanical strength and/or hightemperature characteristics.

Examples of such prior art composites, also called "nanocomposites," aredisclosed in published PCT disclosure WO 93/04118 and U.S. Pat. No.5,385,776, disclosing the admixture of individual platelet particlesderived from intercalated layered silicate materials, with a polymer toform a polymer matrix having one or more properties of the matrixpolymer improved by the addition of the exfoliated intercalate. Asdisclosed in WO 93/04118, the intercalate is formed (the interlayerspacing between adjacent silicate platelets is increased) by adsorptionof a silane coupling agent or an onium cation, such as a quaternaryammonium compound, having a reactive group which is compatible with thematrix polymer. Such quaternary ammonium cations are well known toconvert a highly hydrophilic clay, such as sodium or calciummontmorillonite, into an organophilic clay capable of sorbing organicmolecules.

A publication that discloses direct intercalation (without solvent) ofpolystyrene and poly(ethylene oxide) in organically modified silicatesis Richard A. Vaia et al., "Synthesis and Properties of Two-DimensionalNanostructures by Direct Intercalation of Polymer Melts in LayeredSilicates," Chem. Mater., 5:1694-1696(1993). Also, as disclosed inRichard A. Vaia et al., "New Polymer Electrolyte Nano-composites: MeltIntercalation of Poly(Ethylene Oxide) in Mica-Type Silicates," Adv.Materials, 7, No. 2: (1985), pp. 154-156, poly(ethylene oxide) can beintercalated directly into sodium (Na) montmorillonite and lithium (Li)montmorillonite by heating to 80° C. for 2-6 hours to achieve ad-spacing of 17.7 Å. The intercalation is accompanied by displacingwater molecules, disposed between the clay platelets, with polymermolecules. Apparently, however, the intercalated material could not beexfoliated and was tested in pellet form. It was quite surprising to oneof the authors of these articles that exfoliated material could bemanufactured in accordance with the present invention.

Previous attempts to intercalate polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA) and poly(ethylene oxide) (PEO) between montmorilloniteclay platelets met with little success. As described in Levy et al.,"Interlayer Adsorption of Polyvinylpyrrolidone on Montmorillonite,"Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975,pages 442-450, attempts were made to sorb PVP (40,000 average M.W.)between monoionic montmorillonite clay platelets (Na, K (potassium), Ca(calcium), and Mg (magnesium)) by successive washes with absoluteethanol, and then attempting to sorb the PVP by contact with 1%PVP/ethanol/water solutions, with varying amounts of water (H₂ O), viareplacing the ethanol solvent molecules that were sorbed in washing (toexpand the platelets to about 17.7 Å). Only the sodium montmorillonitehad expanded beyond a 20 Å basal spacing (e.g., 26 Å and 32 Å), at 5+%H₂ O, after contact with the PVP/ethanol/H₂ O solution. It was concludedthat the ethanol was needed to initially increase the basal spacing forlater sorption of PVP, and that water did not directly affect thesorption of PVP between the clay platelets (Table II, page 445), exceptfor sodium montmorillonite. The sorption was time consuming anddifficult and met with little success.

Further, as described in Greenland, "Adsorption of Polyvinyl Alcohols byMontmorillonite," Journal of Colloid Sciences, Vol. 18, pages 647-664(1963), polyvinyl alcohols containing 12% residual acetyl groups couldincrease the basal spacing by only about 10 Å due to the sorbedpolyvinyl alcohol (PVA). As the concentration of polymer in theintercalant polymer-containing solution was increased from 0.25% to 4%,the amount of polymer sorbed was substantially reduced, indicating thatsorption might only be effective at polymer concentrations in theintercalant polymer-containing composition on the order of 1% by weightpolymer, or less. Such a dilute process for intercalation of polymerinto layered materials would be exceptionally costly in drying theintercalated layered materials for separation of intercalate from thepolymer carrier, e.g., water, and, therefore, apparently no further workwas accomplished toward commercialization.

In accordance with one embodiment of the present invention, intercalatesare prepared by contacting a phyllosilicate either with water, or withan aqueous solution of a water-soluble polymer and/or a water-miscibleorganic solvent, like an alcohol, followed by contact with a monomericorganic pesticide compound or a solution of a pesticide compound.Typically, the pesticide compound has a polar organic moiety, such as acarbonyl functionality, like, for example, a carboxylic acid, or saltthereof, an ester, an amide, an aldehyde, a ketone, or a mixturethereof. The pesticide also can contain other polar organic moieties inaddition to, or in place of, the carbonyl functionality, such as, forexample, a sulfur-oxygen moiety, a phosphorus-oxygen moiety, a cyanomoiety, or a nitro moiety. If the intercalate is prepared using anaqueous solution of a water-soluble polymer and/or a water-miscibleorganic solvent, then nonpolar pesticides, like chlordane and lindane,can be intercalated between clay platelets.

The addition of a pesticide or pesticide solution displaces the waterand water-soluble polymer, if present, disposed between the clayplatelets of the intercalate. The pesticide, therefore, displaces thewater and water-soluble polymer between the clay platelets. Theintercalated pesticide then is dried to remove the water, and pelletizedto provide a granular pesticide containing up to 40% by weight of apesticide.

In accordance with an important feature of the present invention, bestresults are achieved by using an aqueous solution of a water-solublepolymer, like polyvinylalcohol, and/or a water-miscible organic solvent,to first intercalate, i.e., activate, the clay, then using an organicpesticide compound having at least one polar organic moiety, andpreferably a carbonyl functionality, in a concentration of at leastabout 2%, preferably at least about 5%, more preferably at least about10%, by weight, based on the weight of organic pesticide compound andcarrier (e.g., water, an organic solvent for the pesticide compound, ora mixture thereof) to achieve better sorption of the organic pesticidecompound between phyllosilicate platelets. If the pesticide is a solidat intercalating temperature, it can be dissolved in a solvent. If thepesticide is a liquid compound at intercalating temperature, thepesticide can be intercalated between phyllosilicate platelets withoutusing a solvent.

Regardless of the concentration of organic pesticide compound in asolvent, a water-soluble polymer:layered material ratio of at least1:20, preferably at least 1:10, more preferably at least 1:4, and mostpreferably about 1:2, by weight, achieves efficient intercalation of theorganic pesticide compound between adjacent platelets of the layeredmaterial. A water-miscible organic solvent can be used in place of thewater-soluble polymer. It has been theorized that water, or aqueoussolution of water-soluble polymer, intercalates between the clay layersto activate the clay, then the organic pesticide compound displaces thewater and water-soluble polymer and is bonded to the silicate plateletsvia chelation-type bonding with the exchangeable cation, or viaelectrostatic or dipole/dipole bonding. The sorption of the water and/orwater-soluble polymer, causes separation or added spacing betweenadjacent silicate platelets. An extrusion process acceleratesintercalation of the pesticide between activated clay platelets.

For simplicity of description, all organic pesticide compounds arehereinafter termed an "intercalant pesticide." The water-solublepolymers are hereinafter termed an "intercalant polymer." In thismanner, the water-soluble polymers, and subsequently the organicpesticides, are sufficiently sorbed to increase the interlayer spacingof the phyllosilicate in the range of about 5 Å to about 100 Å,preferably at least about 10 Å, for easier and more completeexfoliation, if desired, in a commercially viable process, regardless ofthe particular phyllosilicate or intercalant pesticide.

In accordance with the present invention, it has been found that aphyllosilicate, such as a smectite clay, that has been activated withwater or an aqueous solution of a water-soluble polymer and/or awater-miscible organic solvent, can be intercalated by sorption oforganic pesticide compounds having a polar moiety, like carbonylfunctionality, to provide bonding of the polar moiety to the internalsurfaces of the layered material by a mechanism selected from the groupconsisting of ionic complexing, electrostatic complexing, chelation,hydrogen bonding, dipole/dipole interaction, Van Der Waals forces, andany combination thereof. Such bonding between the polar moieties of oneor two intercalant pesticide molecules and the metal cations bonded tothe inner surfaces of the phyllosilicate platelets provides adherencebetween the organic pesticide molecules and the platelet inner surfacesof the layered material. Activation of the clay and sorption and bondingof a platelet metal cation between two electronegative atoms of theintercalant pesticide molecules, like oxygen, sulfur, or nitrogen, forexample, increases the interlayer spacing between adjacent silicateplatelets or other layered material to at least about 5 Å, preferably toat least about 10 Å, and more preferably at least about 20 Å, and mostpreferably in the range of about 30 Å to about 100 Å. In addition, if awater-soluble polymer is used to activate the phyllosilicate, theintercalant polymer provides sufficient interlayer spacing such thatpesticides lacking a polar group can be intercalated into the clay.

The intercalated clay containing a pesticide, i.e., intercalatedpesticide product, can be used directly as a pesticide product. Theintercalated pesticide also can be used as the active ingredient in agranular, dust, or wettable powder pesticide composition by admixture ofthe solid pesticide intercalant with ingredients well known in the art.

Such intercalated pesticides also easily can be exfoliated, if desired,into individual phyllosilicate platelets before or during admixture witha liquid carrier or solvent, for example, one or more monohydricalcohols, such as methanol, ethanol, propanol, and/or butanol,polyhydric alcohols, such as glycerols and glycols, e.g., ethyleneglycol, propylene glycol, butylene glycol, glycerine, and mixturesthereof, aldehydes, ketones, carboxylic acid esters, amines,hydroxyethers, like ethylene glycol monobutyl ether, glycol etheresters, like cellosolve acetate, aromatic or aliphatic hydrocarbons, andother organic solvents, like DMSO, DMF, or HMPA. The exfoliatedplatelets can be used for delivery of any active hydrophobic orhydrophilic organic pesticide compound, such as a contact or a systemicpesticide compound, dissolved or dispersed in the carrier or solvent toprovide either a solid, as a granular, dust, or wettable powder, or athixotropic composition.

DEFINITIONS

Whenever used in this specification, the terms set forth shall have thefollowing meanings:

"Layered material" shall mean an inorganic material, such as a smectiteclay mineral, that is in the form of a plurality of adjacent, boundlayers and has a thickness, for each layer, of about 3 Å to about 50 Å,preferably about 10 Å.

"Platelets" shall mean individual layers of the layered material.

"Intercalate" or "Intercalated" shall mean a layered material thatincludes a water-soluble polymer or an organic pesticide compounddisposed between adjacent platelets of the layered material to increasethe interlayer spacing between the adjacent platelets to at least about5 Å, preferably at least about 10 Å.

"Intercalated Pesticide Product" shall mean an intercalated claycontaining a pesticide.

"Intercalation" shall mean a process for forming an intercalate.

"Intercalant Pesticide" shall mean a pesticide compound having a polarmoiety that is sorbed between platelets of the layered material andcomplexes with the platelet surfaces to form an intercalate.

"Intercalant Polymer" shall mean a water-soluble polymer that is sorbedbetween platelets of the layer material, expands the space between theplatelet materials, and complexes with the platelet surfaces to form anintercalate.

"Intercalating Carrier" shall mean a carrier comprising water with orwithout an organic solvent used together with an intercalant pesticideto form an intercalating composition capable of achieving intercalationof the layered material.

"Intercalating Composition" shall mean a composition comprising anintercalant pesticide, an intercalating carrier for the intercalantpesticide, and a layered material.

"Exfoliate" or "Exfoliated" shall mean individual platelets of anintercalated layered material so that adjacent platelets of theintercalated layered material can be dispersed individually throughout acarrier material, such as a solid carrier, water, an alcohol or glycol,or any other organic solvent.

"Exfoliation" shall mean a process for forming an exfoliate from anintercalate.

SUMMARY OF THE INVENTION

In brief, the present invention is directed to intercalates, and toexfoliates therefrom, formed by contacting a layered phyllosilicate withwater or an aqueous solution of a water-soluble polymer and/or awater-miscible organic solvent, and with an organic pesticide (i.e.,intercalant pesticide), typically having at least one polar moiety, tosorb or intercalate the intercalant pesticide, or mixture of intercalantpesticides, between adjacent phyllosilicate platelets. Sufficientintercalant pesticide is sorbed between adjacent phyllosilicateplatelets to expand the spacing between adjacent platelets (interlayerspacing) to a distance of at least about 5 Å, preferably to at leastabout 10 Å (as measured after water removal, to a maximum water contentof 5% by weight, based on the dry weight of the layered material) andmore preferably in the range of about 20 Å to about 45 Å. Theintercalate, after drying, contains up to about 40% by weight pesticide.If desired, the intercalate can be exfoliated easily, sometimesnaturally, i.e., without shearing. At times, the intercalate requiresshearing that can be accomplished easily, e.g., when mixing theintercalate with an organic solvent carrier, such as an organichydrocarbon, the platelets are obtained by exfoliation of theintercalated phyllosilicate.

The intercalant pesticide has an affinity for the phyllosilicate so thatit expels water and intercalant polymer, is sorbed between silicateplatelets, and is maintained associated with the silicate platelets inthe interlayer spaces, even after exfoliation. In accordance with thepresent invention, the intercalant pesticide typically includes a polarmoiety, for example a carbonyl functionality, like a carboxylic acid, tobe sufficiently bound between clay platelets by a mechanism selectedfrom the group consisting of ionic complexing, electrostatic complexing,chelation, hydrogen bonding, dipole/dipole interactions, Van Der Waalsforces, and any combination thereof. However, the pesticide can be freeof a polar moiety if the phyllosilicate first is activated by contactwith an aqueous solution of a water-soluble polymer, i.e., anintercalant polymer.

Such bonding, via metal cations of the phyllosilicate sharing electronswith two electronegative atoms of one intercalant pesticide molecule orwith two adjacent intercalant pesticide molecules, to an inner surfaceof the phyllosilicate platelets provides adherence between the pesticidemolecules and the platelet inner surfaces of the layered material. Theelectronegative atoms can be, for example, oxygen, sulfur, nitrogen, andcombinations thereof. Atoms having a sufficient electronegativity tobond to metal cations on the inner surface of the platelets preferablyhave an electronegativity of at least 2.0, and more preferably at least2.5 on the Pauling Scale. A "polar moiety" or "polar group" is definedas a moiety having two adjacent atoms that are bonded covalently andpreferably have a difference in electronegativity of at least 0.5electronegativity units on the Pauling Scale. Intercalant pesticideshaving a polar moiety have sufficient affinity for the phyllosilicateplatelets to maintain sufficient interlayer spacing for exfoliation,without the need for coupling agents or spacing agents, such as theonium ion or silane coupling agents disclosed in the above-mentionedprior art. Intercalant pesticides lacking a polar moiety enter the spacebetween two adjacent platelets because of the relatively large spacingprovided by an intercalant polymer during activation of the clay.

A schematic representation of the charge distribution on the surfaces ofa sodium montmorillonite clay is shown in FIGS. 1-3. As shown in FIGS. 2and 3, the location of surface Na (sodium) cations with respect to thelocation of O_(x) (oxygen), Mg (magnesium), Si (silicon), and Al(aluminum) atoms (FIGS. 1 and 2) results in a clay surface chargedistribution as schematically shown in FIG. 3. The positive-negativecharge distribution over the entire clay surface provides for excellentdipole-dipole attraction of pesticide compounds having a polar moiety onthe surfaces of the clay platelets.

Intercalate-containing and/or exfoliate-containing compositions can bein the form of a solid, or a viscous liquid or stable thixotropic gel,that is not subject to phase separation. Either form can be used todeliver the active pesticide compound. In either form, the layeredmaterial is activated, then intercalated by contact with an intercalantpesticide, by mixing and/or extruding, to intercalate the pesticidebetween adjacent phyllosilicate platelets, and finally, optionally,separating (i.e., exfoliating) the intercalated layered material intoindividual platelets.

The amount of water and intercalant polymer used during the activationprocess varies, depending upon the amount of shear imparted to thelayered material during contact with the intercalant pesticide andsolvent. In one method, the layered material is pug milled or extrudedat a water content (with or without a water-soluble polymer) of about25% by weight to about 50% by weight water, preferably about 35% toabout 40% by weight water, based on the dry weight of the layeredmaterial, e.g., clay. Typically, a water-miscible organic solvent ispresent to assist the water activate the clay. An organic solvent oftenis not present if a water-soluble polymer is used.

In another method, the clay and water (or aqueous solution ofintercalant polymer and/or water-miscible organic solvent) are slurried,with at least about 25% by weight water, preferably at least about 65%by weight water, based on the dry weight of the layered material, e.g.,preferably less than about 20% by weight clay in water, based on thetotal weight of layered material and water, more preferably less thanabout 10% layered material in water, with the subsequent addition ofabout 2% by weight to about 90% by weight intercalant pesticide, basedon the dry weight of the layered material, after activation of the clay.

Activation of the clay and sorption of the intercalant pesticide shouldbe sufficient to achieve expansion of adjacent platelets of the layeredmaterial (when measured dry) to an interlayer spacing of at least about5 Å, preferably to a spacing of at least about 10 Å, more preferably aspacing of at least about 20 Å, and most preferably a spacing of about30 Å to about 45 Å. To achieve intercalates that can be exfoliatedeasily using the pesticide intercalants disclosed herein, the weightratio of intercalant pesticide to layered material, preferably awater-swellable smectite clay such as sodium bentonite, in theintercalating composition should be at least about 1:20, preferably atleast about 1:12 to 1:10, more preferably at least about 1:4, and mostpreferably about 1:3. It is preferred that the concentration ofintercalant pesticide, based on the total weight of intercalantpesticide plus intercalant carrier (i.e., water plus any organic liquidsolvent) is at least about 15% by weight, more preferably at least about20% by weight, intercalant pesticide, for example about 20% to about 90%by weight intercalant pesticide, based on the weight of intercalantpesticide plus intercalant carrier during intercalation.

The intercalates of the present invention are increased in interlayerspacing step-wise. If the phyllosilicate is contacted with anintercalant polymer-containing or an intercalant pesticide-containingcomposition containing less than about 16% by weight intercalant polymeror pesticide, e.g., 10% to about 15% by weight, based on the dry weightof the phyllosilicate, a monolayer width of intercalant polymer orpesticide is sorbed (i.e., intercalated) between the adjacent plateletsof the layered material. A monolayer of intercalant intercalated betweenplatelets increases the interlayer spacing to about 5 Å to less thanabout 10 Å. When the amount of intercalant pesticide, or intercalantpolymer, is in the range of about 16% to less than about 35% by weight,based on the weight of the dry layered material, the intercalant issorbed in a bilayer, thereby increasing the interlayer spacing to about10 Å to about 16 Å. At an intercalant pesticide, or intercalant polymer,loading of about 35% to less than about 55% intercalant, based on thedry weight of the layered material contacted, the interlayer spacing isincreased to about 20 Å to about 25 Å, corresponding to three layers ofintercalant sorbed between adjacent platelets of the layered material.At an intercalant loading of about 55% to about 80% intercalant, basedon the dry weight of the layered material, the interlayer spacing willbe increased to about 30 Å to about 35 Å, corresponding to 4 and 5layers of intercalant sorbed (i.e., intercalated) between adjacentplatelets of the layered material.

Such interlayer spacings have never been achieved by directintercalation of intercalant polymers or intercalant pesticides, withoutprior sorption of an onium or silane coupling agent, and provides easierand more complete exfoliation for, or during, incorporation of theplatelets into a carrier or solvent, to provide unexpectedly viscousliquid compositions for delivery of an active pesticide that isdispersed in the carrier or solvent. Such compositions, especially thehigh viscosity thixotropic gels, are particularly useful pesticidecompositions because the environmental and toxicological dangersassociated with spills and spill clean-up of liquid pesticides areovercome. The thixotropic, high viscosity gels are easy to confine andcollect if spilled. In addition, the thixotropic gels can be dissolvedor dispersed in an appropriate solvent by a pesticide applicator toprovide a spray solution.

After exfoliation of the intercalates, the platelets of the intercalateare predominantly completely separated into individual platelets and theoriginally adjacent platelets no longer are retained in a parallel,spaced disposition, but are free to move as predominantly individualintercalant pesticide-coated (either continuously or discontinuously)platelets throughout a carrier or solvent material to maintain viscosityand thixotropy of the carrier material. The predominantly individualphyllosilicate platelets, having their platelet surfaces complexed withintercalant pesticide molecules, are randomly, homogeneously anduniformly dispersed, predominantly as individual platelets, throughoutthe carrier or solvent to achieve new and unexpected viscosities in thecarrier/platelet compositions even after addition of additional activeorganic compounds, such as a second pesticide or a pesticide adjuvant,for administration of the intercalant pesticide and additional activeorganic compounds from the composition.

As recognized, the thickness of the exfoliated, individual platelets(about 10 Å) is relatively small compared to the size of the flatopposite platelet faces. The platelets have an aspect ratio in the rangeof about 200 to about 2,000. Dispersing such finely divided plateletparticles into an organic liquid carrier imparts a very large area ofcontact between carrier and platelet particles, for a given volume ofparticles, and a high degree of platelet homogeneity in the composition.Platelet particles of high strength and modulus, dispersed at sub-micronsize (nanoscale), impart a higher viscosity to an organic liquid carrierthan do comparable loadings of conventional particles of micron size.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a top view (ab-projection) oftwo layers of sodium montmorillonite clay showing the upper oxygen atomsof silicon tetrahedral sheet with sodium cations in hexagonal holes andoctahedral cations of aluminum and magnesium;

FIG. 2 is a side view (bc-projection) of the schematic representation oftwo smectite layers FIG. 1;

FIG. 3 is a schematic representation of the charge distribution on thesurfaces of sodium montmorillonite clay platelets showing thedistribution of positive and negative charges on the clay plateletsurfaces as a result of the natural disposition of the Na, Mg, Al, Si,and O atoms of the clay shown in FIGS. 1 and 2;

FIG. 4 is a graph plotting interlayer space for polyvinylpyrrolidone(PVP):smectite clay complexes (intercalates) showing d(001) and d(002)spacings, in Angstroms (Å), versus percentage of PVP sorbed, based onthe dry weight of the smectite clay;

FIG. 5 is a graph plotting interlayer space for polyvinylalcohol(PVA):smectite clay complexes (intercalates) showing d(001) spacing, inAngstroms, between smectite clay platelets versus percentage of PVAsorbed, based on the dry weight of the smectite clay;

FIG. 6 is an x-ray diffraction pattern for a complex of PVP (weightaverage molecular weight of 10,000):sodium montmorillonite clay, inAngstroms, at a weight ratio of PVP:clay of 20:80;

FIG. 7 is an x-ray diffraction pattern for a complex of PVP (weightaverage molecular weight of 40,000):sodium montmorillonite clay, inAngstroms, at a weight ratio of PVP:clay of 20:80;

FIG. 8 is an x-ray diffraction pattern for a complex of PVA (weightaverage molecular weight of 15,000):sodium montmorillonite clay, inAngstroms, at a weight ratio of PVA:clay of 20:80;

FIG. 9 is an x-ray diffraction pattern for a complex of PVP:sodiummontmorillonite clay, in Angstroms, at a weight ratio of PVP:clay of20:80 (upper pattern), and an x-ray diffraction pattern for about sodiummontmorillonite clay having a crystobalite impurity (lower pattern);

FIG. 10 is an x-ray diffraction pattern for a complex of PVP:sodiummontmorillonite clay, in Angstroms, at a weight ratio of PVP:clay of50:50 (upper pattern), and an x-ray diffraction pattern for about 100%sodium montmorillonite clay having a crystobalite impurity (lowerpattern);

FIG. 11 is an x-ray diffraction pattern for untreated sodiummontmorillonite clay, in Angstroms;

FIG. 12 is a portion of an x-ray diffraction pattern for PVP:sodiummontmorillonite clay, in Angstroms, at a PVP:clay ratio of 80:20,showing a PVP:clay complex peak or d(001) spacing of about 41 Å;

FIGS. 13 and 14 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #1;

FIGS. 15 and 16 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #9a;

FIGS. 17 and 18 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #9b;

FIGS. 19 and 20 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #10d;

FIGS. 21 and 22 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #11c;

FIGS. 23 and 24 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #12a;

FIGS. 25 and 26 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #12b;

FIGS. 27 and 28 are x-ray diffraction patterns, respectively, of wet anddry samples of Example #12c; and

FIGS. 29 and 30 are x-ray diffraction patterns, respectively, of wet anddry samples of Examples #13a-d.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

To form the intercalated and, optionally, exfoliated pesticides of thepresent invention, the layered material, e.g., the phyllosilicate, isactivated, i.e., swelled or intercalated, by water, an intercalantpolymer, a water-miscible organic solvent, or mixture thereof, followedby sorption of an intercalant pesticide. In accordance with a preferredembodiment of the present invention, the activated phyllosilicateincludes at least 4% by weight water, up to about 5,000% by weightwater, based on the dry weight of the phyllosilicate, preferably about7% to about 100% water, more preferably about 25% to about 50% by weightwater, prior to or during contact with the intercalant pesticide toachieve sufficient intercalation, especially if the pesticideintercalate will be exfoliated. Preferably, the phyllosilicate includesat least about 4% by weight water before contact with the intercalantpesticide for efficient intercalation.

The amount of intercalant pesticide in contact with the phyllosilicate,especially for efficient exfoliation, should provide an intercalantpesticide/phyllosilicate weight ratio (based on the dry weight of thephyllosilicate) of at least about 1:20, preferably at least about 3:20,and more preferably about 4-14:20, to provide efficient sorption andcomplexing (i.e., intercalation) of the intercalant pesticide betweenthe platelets of the layered material, e.g., phyllosilicate.Intercalation of the intercalant pesticide, especially nonpolarintercalant pesticides, is facilitated by using an intercalant polymerand water to activate the phyllosilicate.

The intercalant pesticides are introduced in the form of a solid orliquid composition (neat or aqueous, with or without a polar or nonpolarorganic solvent, e.g., an aliphatic hydrocarbon, such as heptane) havingan intercalant pesticide concentration of at least about 2%, preferablyat least about 5%, more preferably at least about 10%, and mostpreferably at least about 50% to about 100% by weight intercalantpesticide, based on the weight of the pesticide compound and carrier,for intercalant pesticide sorption. The intercalant pesticide can beadded as a solid with the addition to the layered material/intercalantpesticide blend of about 20% water, preferably at least about 30% waterto about 5,000% water or more, based on the dry weight of layeredmaterial.

Preferably about 30% to about 50% water, more preferably about 30% toabout 40% by weight water, based on the dry weight of the layeredmaterial, is used when extruding or pug milling, so that less water issorbed by the intercalate, thereby necessitating less drying energyafter intercalation. The pesticide intercalants can be introduced intothe spaces between every layer, nearly every layer, or at least apredominance of the layers of the layered material such that theplatelet particles, if subsequently exfoliated, are preferablypredominantly less than about 5 layers in thickness, more preferably,predominantly about 1 or 2 layers in thickness, and most preferably,predominantly single platelets.

Any swellable layered material that sufficiently sorbs the intercalantpesticide to increase the interlayer spacing between adjacentphyllosilicate platelets to at least about 10 Å (when the phyllosilicateis measured dry) can be used in the practice of this invention. Usefulswellable layered materials include phyllosilicates, such as smectiteclay minerals, e.g., montmorillonite, particularly sodiummontmorillonite, magnesium montmorillonite and/or calciummontmorillonite, nontronite, beidellite, volkonskoite, hectorite,saponite, sauconite, sobockite, stevensite, svinfordite, vermiculite,and the like. Other useful layered materials include micaceous minerals,such as illite and mixed layered illite/smectite minerals, such asrectorite, tarosovite, ledikite and admixtures of illites with the clayminerals named above.

Other layered materials having little or no charge on the layers can beused in this invention provided they can be intercalated with theintercalant pesticides to expand their interlayer spacing to at leastabout 5 Å, preferably at least about 10 Å. Preferred swellable layeredmaterials are phyllosilicates of the 2:1 type having a negative chargeon the layers ranging from about 0.15 to about 0.9 charges per formulaunit and a commensurate number of exchangeable metal cations in theinterlayer spaces. Most preferred layered materials are smectite clayminerals such as montmorillonite, nontronite, beidellite, volkonskoite,hectorite, saponite, sauconite, sobockite, stevensite, and svinfordite.

As used herein the "interlayer spacing" refers to the distance betweenthe internal faces of the adjacent layers as they are assembled in thelayered material before any delamination (i.e., exfoliation) takesplace. The interlayer spacing is measured when the layered material is"air dry," i.e., contains 3-10% by weight water, preferably about 3-6%by weight water, e.g., 5% by weight water based on the dry weight of thelayered material. The preferred clay materials generally includeinterlayer cations such as Li⁺ (lithium), Na⁺, Ca⁺² (calcium), K⁺(potassium) M⁺², NH₄ ⁺ (ammonium), and the like, including mixturesthereof.

In accordance with a preferred embodiment of the present invention, thephyllosilicate is contacted with an aqueous solution of an intercalantpolymer to provide a sufficient spacing between adjacent platelets topermit intercalation of polar and/or nonpolar pesticides. Theintercalant polymer should be water soluble (herein defined assufficiently soluble such that at least 0.1 gram of the polymer willdissolve per 100 grams of distilled water at 25° C.). In accordance witha preferred embodiment of the present invention, the intercalant polymerincludes a functionality selected from the group consisting of acarbonyl, carboxyl, hydroxyl, amine, amide, ether, ester, sulfate,sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate, oran aromatic ring to be sufficiently complexed or bound to the plateletsurfaces of the layered material. Such intercalant polymers havesufficient affinity for the phyllosilicate platelets to providesufficient interlayer spacing for exfoliation, e.g., about 5 Å to about100 Å, preferably about 10 Å to about 50 Å, and to maintain attachmentto the surfaces of the platelets, without the need for coupling agentsor spacing agents, such as the onium ion or silane coupling agentsdisclosed in the above-mentioned prior art.

Sorption of the intercalant polymer should be sufficient to achieveexpansion of adjacent platelets of the layered material (when measureddry, i.e., having a maximum of about 5% by weight water) to aninterlayer spacing of at least about 5 Å, preferably a spacing of atleast about 10 Å, more preferably a spacing of at least about 20 Å, andmost preferably a spacing of about 30-45 Å. To achieve intercalates thateasily incorporate a nonpolar pesticide or that can be exfoliated easilyusing the preferred water-soluble polymer intercalants disclosed herein,such as polyvinylpyrrolidone, polyvinyl alcohol, and mixtures thereof,the weight ratio of intercalant polymer to layered material, preferablya water-swellable smectite clay such as sodium bentonite, in theintercalating composition contacting the phyllosilicate should be atleast about 1:20, preferably at least about 1:12 to 1:10, morepreferably at least about 1:4, and most preferably about 1:3 to about1:2. It is preferred that the concentration of polymer, based on thetotal weight of intercalant polymer plus intercalant carrier (water plusany organic liquid solvent) is at least about 15% by weight, morepreferably at least about 20% by weight polymer, for example about20%-30% to about 90% by weight polymer, based on the weight of polymerplus intercalant carrier (water plus any organic solvent) duringintercalation.

In accordance with a preferred embodiment of the present invention, thecombination of layered material and aqueous solution containing anintercalant polymer includes at least about 4% by weight water, up toabout 5000% by weight water, based on the dry weight of thephyllosilicate, preferably about 7% to about 100% water, more preferablyabout 25% to about 50% by weight water, prior to or during contact withthe intercalant polymer to achieve sufficient polymer intercalation.Preferably, the phyllosilicate includes at least about 4% by weightwater before contact with the polymer for efficient intercalation. Theamount of intercalant polymer in contact with the phyllosilicate forefficient exfoliation, should provide efficient sorption and complexing(intercalation) of the polymer between the platelets of the layeredmaterial, preferably about 16 to about 70 percent by weight intercalantpolymer, based on the dry weight of the layered silicate material.

The preferred intercalant polymers are water-soluble and are added inthe form of a solid or liquid (neat or aqueous solution or dispersion,with or without a liquid organic solvent, e.g., alcohol) having anintercalant polymer concentration of at least about 2%, preferably atleast about 5%, more preferably at least about 50% to about 100%, byweight intercalant polymer, based on the dry weight of the layeredmaterial, for intercalant polymer sorption. The polymer can be added asa solid with the addition to the layered material/polymer blend of atleast about 20% water, preferably at least about 30% water to about5000% water or more, based on the dry weight of the layered material,with or without another solvent for the intercalant polymer, preferablyabout 30% to about 50% water, more preferably about 30% to about 40%.The intercalant polymer can be introduced into the spaces between everylayer, nearly every layer, or at least a predominance of the layers ofthe layered material such that the subsequently exfoliated plateletparticles are preferably, predominantly less than about 5 layers inthickness, more preferably, predominantly about 1 or 2 layers inthickness, and most preferably, predominantly single platelets.

The amount of intercalant polymer intercalated into the swellablelayered materials useful in this invention, in order that nonpolarpesticide compounds can intercalate in the layered material, and suchthat the layered material can be easily exfoliated or delaminated intoindividual platelets, can vary substantially between about 10% and about80%, based on the dry weight of the layered silicate material. In thepreferred embodiments of the invention, amounts of intercalants polymersemployed, with respect to the dry weight of layered material beingintercalated, preferably range from about 8 grams of intercalantpolymer/100 grams of layered material (dry basis), preferably at leastabout 10 grams of polymer/100 grams of layered material, to about 80 toabout 90 grams intercalant polymer/100 grams of layered material. Morepreferred amounts are from about 20 grams intercalant polymer/100 gramsof layered material to about 60 grams intercalant polymer/100 grams oflayered material (dry basis).

The polymer intercalants are introduced into (i.e., sorbed within) theinterlayer spaces of the layered material in one of two ways. In apreferred method of intercalating, the layered material and anintercalant polymer or intercalant polymer/water solution, orintercalant polymer, water and an organic solvent, are intimately mixed,e.g., by extrusion or pug milling. To achieve sufficient intercalationfor exfoliation, the layered material/intercalant polymer blend containsat least about 8%, preferably at least about 10%, by weight intercalantpolymer, based on the dry weight of the layered material. Theintercalating carrier (preferably water, with or without an organicsolvent) can be added by first solubilizing or dispersing theintercalant polymer in the carrier, or the dry intercalant polymer andrelatively dry phyllosilicate (preferably containing at least about 4%by weight water) can be blended and the intercalating carrier added tothe blend, or to the phyllosilicate prior to adding the dry intercalantpolymer. In every case, it has been found that surprising sorption andcomplexing of intercalant polymer between platelets is achieved atrelatively low loadings of intercalating carrier, especially water,e.g., at least about 4% by weight water, based on the dry weight of thephyllosilicate. When intercalating the phyllosilicate in slurry form(e.g., 900 pounds water, 100 pounds phyllosillicate, 25 pounds polymer)the amount of water can vary from a preferred minimum of at least about30% by weight water, with no upper limit to the amount of water (thephyllosilicate intercalate is easily separated from the intercalatingcomposition).

Alternatively, the intercalating carrier, e.g., water, with or withoutan organic solvent, can be added directly to the phyllosilicate prior toadding the intercalant polymer, either dry or in solution. Sorption ofthe intercalant polymer molecules can be performed by exposing thelayered material to dry or liquid intercalant polymer compositionscontaining at least about 2%, preferably at least about 5%, by weightintercalant polymer, more preferably at least about 50% intercalantpolymer, based on the dry weight of the layered material. Sorption canbe aided by exposure of the intercalating composition to heat, pressure,ultrasonic cavitation, or microwaves.

In accordance with another method of intercalating the intercalantpolymer between the platelets of the layered material and exfoliatingthe intercalate, the layered material, containing at least about 4% byweight water, preferably about 10% to about 15% by weight water, isblended with an aqueous solution of a water-soluble intercalant polymerin a ratio sufficient to provide at least about 8% by weight, preferablyat least about 10% by weight, intercalant polymer, based on the dryweight of the layered material. The blend then preferably is extrudedfor faster intercation of the polymer with the layered material.

The preferred intercalant polymers are water-soluble, such aspolyvinylpyrrolidone (PVP) having a repeating structure (I) as follows:##STR1## wherein n is a number from 2 to about 1500. Thewater-solubility of PVP can be adjusted according to (1) the degree ofhydrolysis of the polyvinylpyrrolidone, and (2) by forming a metal saltof PVP, such as sodium or potassium. PVP can be hydrolyzed to thestructure (II): ##STR2## and the PVP, or copolymers of vinylpyrrolidoneand a vinyl amide of γ-amine butyric acid, can be intercalated in thesalt form, e.g., sodium or potassium polyvinylpyrrolidone polymers.Preferred PVP intercalants, and the following PVP derivatives, have aweight average molecular weight in the range of about 210 to about100,000 or more, more preferably about 1,000 to about 40,000.

Other suitable water-soluble vinyl polymers include poly(vinyl alcohol)##STR3## The polyvinyl alcohols (PVA) function best when they areessentially fully hydrolyzed, e.g., 5% or less acetyl groups, preferably1% or less residual acetyl groups. A lower molecular weight PVAfunctions best, e.g., a weight average molecular weight of about 2,000to about 10,000, but higher molecular weight PVA also functions, e.g.,up to about 100,000.

The polyacrylic acid polymers and copolymers, and partially or fullyneutralized salts, e.g., metal salts, are also suitable, having monomerunits: ##STR4## and are commercially available as CARBOPOL resins fromB. F. Goodrich and PRIMAL resins from Rohm & Haas. Light cross-linkingis acceptable, as long as water solubility is retained. Weight averagemolecular weights for the polyacrylic polymers and copolymers describedabove and below of about 10,000 or less, e.g., about 200 to about10,000, intercalate more easily, but higher molecular weight polymers,up to about 100,000 or more, also function.

Other water-soluble derivatives of, and substituted, polyacrylic acidsalso are useful as intercalant polymers in accordance with the presentinvention, such as poly(methacrylic acid) (PMAA), having a repeatingmonomeric structure: ##STR5##

Similar water-soluble polymers and copolymers that are suitable inaccordance with the present invention include poly(methacrylamide), orPMAAm, having a general repeating monomeric structure: ##STR6##Poly(N,N-dimethylacrylamide), having the gener-al repeating monomericstructure: ##STR7##

Poly(N-isopropylacrylamide), or PIPAAm, having the general repeatingmonomeric structure: ##STR8## Poly(N-acetamidoacrylamide) having ageneral repeating monomeric structure: ##STR9## andpoly(N-acetmidomethacrylamide) having a general repeating monomericstructure: ##STR10## Water-soluble copolymers including any one or moreof the above-described acrylic polymers also are useful in accordancewith the principles of the present invention, including the acrylicinterpolymers of polyacrylic acid and poly(methacrylic acid),polyacrylic acid with poly-(methacrylamide), and polyacrylic acid withmethacrylic acid.

Other suitable water-soluble polymers include polyvinyloxazolidone (PVO)and polyvinylmethyloxazolidone (PVMO), having the general repeatingmonomeric structures: ##STR11## Also suitable arepolyoxypropylene-polyoxyethylene block polymers that conform to theformulas: ##STR12## wherein x and z are each an integer in the range ofabout 4 to about 30, and y is an integer in the range of about 4 toabout 100, for example Meroxapol 105, Meroxapol 108, Meroxapol 171,Meroxapol 172, Meroxapol 174, Meroxapol 178, Meroxapol 251, Meroxapol252, Meroxapol 254, Meroxapol 255, Meroxapol 258, Meroxapol 311,Meroxapol 312, and Meroxapol 314.

Other suitable water-soluble/water-dispersible intercalant polymersinclude, but are not limited to, polyacrylamide and copolymers ofacrylamide, acrylamide/sodium acrylate copolymer, acrylate/acrylamidecopolymer, acrylate/ammonium methacrylate copolymer,acrylate/diacetoneacrylamide copolymers, acrylic/acrylate copolymers,adipic acid/dimethylaminohydroxypropyl diethylenetriamine copolymer,ammonium acrylate copolymers, ammonium styrene/acrylate copolymers,ammonium vinyl acetate/acrylate copolymers, AMPacrylate/diacetoneacrylamide copolymers, AMPDacrylate/diacetoneacrylamide copolymers, butyl benzoic acid/phthalicanhydride/trimethylolethane copolymer, cornstarch/acrylamide/sodiumacrylate copolymer, diethylene glycolamine/epichlorohydrin/piperazinecopolymer, dodecanedioic acid/cetearyl alcohol/glycol copolymers,ethylene/vinyl alcohol copolymer, ethyl ester of polyethylenimines (suchas hydroxyethyl/PEI-1000 and hydroxyethyl PEI-1500), isopropyl ester ofPVM/MA copolymer, melamine/formaldehyde resin, methacryloyl ethylbetaine/methacrylate copolymers, methoxy PEG-22/dodecyl glycolcopolymer, octadecene/maleic anhydride copolymer,octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers,octyl-acrylamide/acrylate copolymers, PEG/dodecyl glycol co-polymers,polyethyleneimines (such as PEI-7, PEI-15, PEI-30, PEI-45, PEI-275,PEI-700, PEI-1000, PEI-1500, and PEI-2500), phthalicanhydride/glycerin/glycidyl decanoate copolymer, metal salts of acrylicand polyacrylic acid, polyaminopropyl biguanide, polymeric quaternaryammonium salts (such as polyquaternium-1, polyquaternium-2,poly-quaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7,polyquaternium-8, polyquaternium-9, poly-quaternium-10,polyquaternium-11, polyquaternium-12, polyquaternium-13,polyquaternium-14, and polyquaternium-15), polyvinyl imidazoliniumacetate, potassium polyacrylate, sodium polyacrylate, metal salts ofPVM/MA copolymers, (e.g., Li, K, Na, Ru, Ce salts), PVP/eicosenecopolymers, PVP/ethyl methacrylate/methacrylic acid copolymer,PVP/hexadecene copolymer, PVP/VA copolymer, PVP/vinyl acetate/itaconicacid copolymer, sodium acrylate/vinyl alcohol copolymers, sodium C₄ -C₁₂and other metal salts of olefin/maleic acid copolymers, sodiumpolymethacrylate, sodium polystyrene sulfonate, sodiumstyrene/acrylate/PEG-10 dimaleate copolymer, water-soluble esters andethers of cellulose, sodium styrene/PEG-10 maleate/nonoxynol-10maleate/acrylate copolymer, starch/acrylate/acrylamide copolymers,styrene/acrylamide copolymer, styrene/acrylate/ammonium methacrylatecopolymer, styrene/maleic anhydride copolymer, styrene/PVO copolymer,sucrose benzoate/sucrose acetate isobutyrate/butyl benzyl phthalatecopolymer, sucrose benzoate/sucrose acetate isobutyrate/butylbenzylphthalate/methyl methacrylate copolymer, urea/-formaldehydeprepolymers, urea/melamine/formaldehyde prepolymers, vinylacetate/crotonic acid copolymers, vinyl alcohol copolymers, and mixturesthereof. Other water-soluble polymeric polyols and polyhydric alcohols,such as polysaccharides, also are suitable as polymer intercalants.

After contact between the layered material and water or the aqueoussolution of intercalant polymer and/or water-miscible organic solvent,the resulting composition typically is a paste. An intercalantpesticide, either neat or in solution, then is added to the paste. Thewater and intercalant polymer activated the layered material such thatthe intercalant pesticide now intercalates between surfaces of thelayered material. The pesticide is added as a liquid or as a solid tothe activated layered material, and the resulting mixture typically isextruded to facilitate intercalation of the intercalant pesticide.Alternatively, the layered material, water, optional polymer and organicsolvent, and intercalant pesticide all can be admixed, then extruded.

The amount of intercalant pesticide intercalated into the activatedlayered material varies substantially between about 0.01% and about 40%,and preferably between about 0.1% and 30%, based on the dry weight ofthe layered silicate material. The amount of intercalated pesticidegenerally is an amount sufficient for the pesticide to perform itsintended function. However, high percentages of pesticide can beintercalated to provide a concentrated intercalated pesticide that issubsequently diluted with a liquid or solid carrier to provide apesticide composition. The amount of intercalant pesticide intercalatedinto the layered material, therefore, can be substantially greater thanthe maximum of about 10% by weight pesticide applied to calcined clays.

In preferred embodiments of the invention, the amount of intercalantpesticides employed, with respect to the dry weight of layered materialbeing intercalated, ranges from about 0.1 grams of intercalantpesticide:100 grams of layered material (dry basis), preferably at leastabout 1 gram of intercalant pesticide:100 grams of layered material toabout 40 grams intercalant pesticide:100 grams of layered material. Morepreferred amounts are from about 5 grams intercalant pesticide/100 gramsof layered material to about 30 grams intercalant pesticide/100 grams oflayered material (dry basis). To achieve sufficient intercalation forexfoliation, the layered material/intercalant pesticide blend containsat least about 8% by weight, and preferably at least about 10%, byweight intercalant pesticide, based on the dry weight of the layeredmaterial.

The intercalant pesticides are introduced into (i.e., sorbed within) theinterlayer spaces of the layered material in one of two ways. In apreferred method, the intercalant pesticide is dissolved in a solvent,and the intercalant pesticide solution is admixed with the layeredmaterial either before or after the layered material has been activatedby contact with water or an aqueous solution of an intercalant polymerand/or water-miscible organic solvent. In an alternative method, thepesticide is added in a neat form to the activated layered material. Theresulting mixture is extruded or pug milled to form an intercalatedcompo-sition comprising the activated layered material and anintercalant pesticide. The resulting mixture typically is a paste that,after pesticide intercalation, is dried, then pelletized to form apesticide composition.

The intercalant pesticide carrier (i.e., water, an organic solvent, or amixture thereof) can be added by first solubilizing or dispersing theintercalant pesticide in the carrier, or a dry intercalant pesticide andrelatively dry phyllosilicate (preferably containing at least about 4%by weight water) can be blended and the intercalating carrier added tothe blend, or to the phyllosilicate prior to adding the dry intercalantpesticide. In every case, it has been found that surprising sorption andcomplexing of intercalant pesticide between platelets is achieved atrelatively low loadings of intercalating carrier, especially water,e.g., at least about 4% by weight water, based on the dry weight of thephyllosilicate. When intercalating the phyllosilicate in slurry form,the amount of water can vary from a preferred minimum of at least about30% by weight water, with no upper limit to the amount of water in theintercalating composition (the phyllosilicate intercalate is easilyseparated from the intercalating composition).

Alternatively, the intercalating carrier can be added directly to thephyllosilicate prior to adding the intercalant pesticide, either dry orin solution. Sorption of the intercalant pesticide molecules can beperformed by exposing the layered material to dry or liquid intercalantpesticides in the intercalating composition containing at least about0.01%, preferably at least about 0.1%, more preferably at least about1%, intercalant pesticide, based on the dry weight of the layeredmaterial. Sorption can be aided by exposure of the intercalatingcomposition to heat, pressure, ultrasonic cavitation, or microwaves.

In accordance with another method of intercalating the intercalantpesticide between the platelets of the layered material, and optionallyexfoliating the intercalate, the layered material, containing at leastabout 4%, and preferably about 10% to about 15%, by weight water, isblended with an intercalant pesticide in a ratio sufficient to provideat least about 8% by weight, preferably at least about 10% by weightintercalant pesticide, based on the dry weight of the layered material.The blend then preferably is extruded for faster intercalation of theintercalant pesticide with the layered material.

An intercalant pesticide having a polar moiety has an affinity for thephyllosilicate so that it is sorbed between, and is maintainedassociated with the surfaces of the silicate platelets, in theinterlayer spaces, and after exfoliation. Pesticides lacking a polarmoiety can be intercalated into a layered material that previously hasbeen activated with water and a water-soluble polymer.

In accordance with the present invention, the intercalant pesticidepreferably includes a polar moiety, like a carbonyl functionality, to besufficiently bound, as theorized herein, by a mechanism selected fromthe group consisting of ionic complexing, electrostatic complexing,chelation, hydrogen bonding, dipole/dipole interaction, Van Der Waalsforces, and any combination thereof. Such bonding, via the metal cationsof the phyllosilicate sharing electrons with electronegative atoms of apolar moiety of one intercalant pesticide molecule or of two adjacentintercalant pesticide molecules, to an inner surface of thephyllosilicate platelets provides adherence between the polar moiety andthe platelet inner surfaces of the layered material. Such intercalantpesticides have sufficient affinity for the phyllosilicate platelets tomaintain sufficient interlayer spacing for exfoliation, without the needfor coupling agents or spacing agents, such as the onium ion or silanecoupling agents disclosed in the above-mentioned prior art. Inpesticides lacking a polar moiety, the water-soluble polymer separatesthe platelets of the layered material a sufficient amount to allow thepesticides to intercalate between adjacent layers. The pesticide, eithercontaining or lacking a polar moiety, displaces water and thewater-soluble polymer from the space between adjacent layers of thelayered material.

As shown in FIGS. 1-3, the disposition of surface Na⁺ ions with respectto the disposition of O, Mg, Si, and Al atoms, and the natural claysubstitution of Mg⁺² cations for Al⁺³ cations, leaving a net negativecharge at the sites of substitution, results in a clay surface chargedistribution as shown in FIG. 3. This alternating positive to negativesurface charge over spans of the clay platelets surfaces, and on theclay platelet surfaces in the interlayer spacing, provide for excellentdipole-dipole attraction of pesticide molecules having a polar moietyfor intercalation of the clay, and, after optional exfoliation, forbonding of such polar pesticide molecules on the platelet surfaces.

In accordance with an important feature of the present invention, theintercalated phyllosilicate can be manufactured in a concentrated form,e.g., up to 40%, preferably 1-30%, intercalant pesticide, by weight, and10-90%, preferably 20-80%, intercalated phyllosilicate, by weight, andcan be dispersed in an organic solvent and exfoliated, before or afteraddition to the solvent, to a desired platelet loading.

Pesticides useful in the present invention include insecticides,herbicides, acaricides, growth regulators, rodenticides, defoliants,fungicides, larvacides, nematocides, repellents, and other compoundscapable of repelling, mitigating, or destroying undesirable andobjectionable plants and animals. Preferred pesticides are organiccompounds having at least one polar moiety. Polarity of the moietyresults from two adjacent atoms that are covalently bonded, wherein afirst atom having a low electronegativity is bonded to a second atomhaving a higher electronegativity. The difference in electronegativitybetween the two atoms (e.g., preferably at least about 0.5electronegativity units) creates a charge differential between the firstand second atoms, i.e., polarity. The first atom of lowerelectronegativity generally has an electronegativity of at least 2, thesecond atom of higher electronegativity has an electronegativitypreferably at least 0.5 electronegativity units greater than the firstatom, and typically is an atom such as oxygen, sulfur, or nitrogen.

The polar moiety of the organic pesticide compound often is a carbonylmoiety, such as in a carboxylic acid or salt thereof, an ester, anamide, an anhydride, a ketone, or an aldehyde. However, the polar moietyalso can be cyano, nitro, thiocarbamate, amino, carbamic, phosphate,thiophosphate, sulfoxide, carboximide, urea, sulfone, phosphorothioate,phosphorodithioate, thiourea, dithiocarbamate, phosphoramidodi-thioate,methylsulfonyl, phosphonate, sulfamide, phosphoramide, sulfonate,dithiocarbonate, hydroxyl, sulfate, sulfinate, sulfamate, or phosphinatemoieties, for example. The polar moiety also can be other moietiescontaining a combination of sulfur and oxygen atoms, or a combination ofphosphorus and oxygen atoms.

Organic pesticide compounds containing one or more polar moieties areparticularly suitable for use as intercalant pesticides in accordancewith the present invention. However, pesticides lacking a polar groupalso can be used in the intercalant pesticide when an intercalantpolymer is used to activate the layered material. The following arenonlimiting examples of pesticides useful in the present invention. Thelists are intended to set forth examples of useful pesticides and arenot intended to limit the pesticides that can be used in the presentinvention.

FUNGICIDES

Allyl alcohol, anilazine, triadimenol, benomyl, benquinox, bunema,captafol, captan, carbendazim, carboxin, chinosol, chloroneb,chlorothalonil, cycloheximide, dazomet, dicloran, dichlofluanid,dichlone, dimethirimol, dinocap, manzeb, dithianon, dodemorph, dodine,drazoxolon, edinfenphos, fenaminosulf, fenapanil, fentiazon, ferbam,folpet, fongarid, guazatine, hymexazol, iprodione, kasugamycin, maneb,MEMC, methylthiophenate, metiram, nabam, neo-asozin, o-phenylphenol,PMA, oxycarboxin, parinol, PCNB, phosethyl, piperalin, polyoxin,procymidone, propineb, propazine, propionic acid, prothiocarb,pyracarbolid, pyrazophos, thiabendazole, thiophanate, thiram,tolylfluanid, triadimefon, tridemorph, triforine, triphenyltin acetate,validamycin A, vinclozolin, vondozeb, zineb, chloranil, ziram,8-quinolinol, CDEC, metam, glyodin, 2,6-bisdimethylaminomethyl!cyclohexanone, hexachloroacetone, bromoacetylbromide, picloram, benalaxyl, blasticidin S, bupirimate, buthiobate,chinomethionate, chlozolinate, cymoxanil, cyproconazole, dithianon,ethirimol, etridazole, fenarimol, fenpiclonil, fenpropidin,fenpropimorph, fentin, flusilazole, flutriafol, flutolanl, fuberidazole,furalaxyl, imazalil, imibenconazole, iprobenphos, isoprothiolane,mancozeb, mepronil, methfuroxam, metsulfovax, myclobutanil, nuarimol,ofurace, oxadixyl, polyoxin B, polyoxin D, prochloraz, procymidone,propiconazole, pyroquilon, quintozene, tebucanazole, tetraconazole,triarimol, tricyclazole, triforine, and mixtures thereof, and in mixturewith other pesticides. Salts and esters of these fungicides also can beused as the pesticide.

HERBICIDES

Acifluorfen, alachlor, alanap, alloxydim, ametryn, amitrol, asulam,atrazine, azide, barban, benazolin, benefin, bensulide, bentazone,benthiocarb, benzoylprop, benzthiazuron, bifenox, acetochlor, acrolein,benazolin, buthidazole, allidochlor, bromacil, bromofenoxin, bromoxynil,butachlor, butralin, buturon, butylate, chlometoxynil, chloramben,chlorbromuron, chlorfenprop, chloridazon, chlorotoluron, chloroxuron,chlorpropham, chlorthiamid, CNP, crotoxyphos, cycloate, cyprazine,2,4-D, dalapon, 2,4-DB, DCPA, 2,4-DEP, desmedipham, 2,4-DP, desmetryn,diallate, dicamba, dichlobenil, dichlorprop, diethatyl, difenoxuron,diclofop, dimexano, dinitramine, dinoseb, dinoterb, diphenamid,dipropetryn, diquat, diuron, endothall, erbon, ethofumesate, fenac,fenuron, flamprop, fluchloralin, EPTC, pentachlorophenol, fluometuron,fluorodifen, flurecol, glyphosate, glyphosine, hexazinone, ioxynil,isopropalin, isoproturon, karbutilate, lenacil, linuron, MCPA, MCPB,mecoprop, medinoterb, methazole, methoprotryne, metobromuron,metolachlor, metoxuron, metribuzin, molinate, monalide, monlinuron,monuron, naptalam, neburon, nitralin, nitrofen, norea, norflurazon,oryzalin, oxadiazon, paraquat, pebulate, penoxalin, perfluidone,phenisopham, phenmedipham, picloram, procyazine, profluralin, prometon,prometryn, pronamide, propachlor, propanil, propazine, propham,secbumeton, siduron, silvex, simazine, swep, 2,4,5-T, 2,3,6-TBA,tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutol, terbutryn,tetrafluoron, triallate, trietazine, trifluralin, vernolate,1-naphthaleneacetic acid, N-m-tolylphthalamic acid, ethyl-1-naphthaleneacetate, chloroacetic acid, trichloroacetic acid, p-chloromandelic acid,dimethylamino-2,3,5-triiodobenzoate, 2-naphthoxyacetic acid,phenoxyacetic acid, 2-phenoxypropionic acid, o-chlorophenoxy aceticacid, p-chlorophenoxy acetic acid, MCPA, silvex, MCPB, p-bromophenoxyacetic acid, dimethylamino-4 2,4-dichlorophenoxy!butryate,3-indolebutyric acid, 3-indoleacetic acid, 3-indolepropionic acid,gibberellic acid, N,N-dimethylsuccinamic acid, 2-furanacrylic acid,endothal, 1-naphthaleneacetamide, CDAA, N-methyl-N-1-naphthylacetamide,N-1-naphthyl acetamide, 2- 3-chlorophenoxy!propionamide, noruron,linuron, siduron, metobromuron, terbacil, chloroxuron, aminotriazole,cyanazine, chlorflurenol, chlorsulfuron, cyanazine, cyometrinil,3,6-dichloropicolinic acid, dichlofop, difenzoquat, diphenamid,ethaflualin, ethepon, flurazole, flurenol, fluridone, fosamine, isouron,mefluidide, 1,8-naphthalic anhydride, napropamide, pyrazon, thoibencarb,anilazine, diphenatrile, N- 2,4-dichlorophenoxyl)acetyl-DL-methionine,daminozide, pyrazon, ethoxyquin, propham, EPTC,S-carboxymethyl-N,N-dimethyldicarbamate, phosphan, merphos, ethephon,tricamba, amiben, MCPD, glufosinate, indole-3-butyric acid,β-naphthoxyacetic acid, triclopyr, 9-undecylenic acid, oxyflurofen,dinitrocresol, flurtamone, diflufenican, difunon, fomesafen, clethodim,sethoxydim, haloxyfop, tralkoxydim, fenoxaprop, fluazifop,phaseolotoxin, rhizobitoxine, barban, ethephon, tetcyclacis, mepiquatchloride, ancymidol, uniconzaole, paclobutrazol, diquatop,pendimethalin, karbutilate, asulam, clopyralid, fluroxypyr, chlorimuron,chlorsulfuron, metsulfuron, buthidazole, imazamethabenz, imazapyr,imazaquin, imazethapry, isoxaben, cinmethylin, ethofumesate, andmixtures thereof, and in mixture with other pesticides. Several of theherbicides listed above are acid compounds. In addition to the acid formof such herbicides, esters (e.g., esters derived from C₁ -C₁₂ alcohols)and salts (e.g., amine, potassium, lithium, and sodium salts) of theseherbicides can be used as the intercalant pesticide.

INSECTICIDES AND ACARICIDES

Acephate, aldicarb, aldoxycarb, aldrin, d-trans allethrin, allyxycarb,aminocarb, amitraz, azinphos, azinphos, azocyclotin, azothoate,bendiocarb, benzomate, binapacryl, bomyl, BPMC, bromophos,bromophos-ethyl, bromopropylate, butacarb, butocarboxim, chlordane,chlordecone, heptachlor, lindane, methoxychlor, toxaphene,butoxicarboxim, carbaryl, carbofuran, carbophenothion, cartap,chloridimeform, chlorfenethol, chlorfenvinphos, chlormephos,chlorobenzilate, chloropropylate, chlorphoxim, chlorpyrifos,chlorthiophos, coumaphos, CPMC, crufomate, cryolite, cyanofenphos,cyanophos, cyhexatin, cypermethrin, cythioate, DDT, DDVP, demeton,demeton-S-methyl, dialifor, diazinon, dicofol, dicrotophos, dieldrin,dienochlor, diflubenzuron, dimefox, dimethoate, dimethrin, dinobuton,dioxacarb, dioxathion, disulfoton, DNOC, d-phenothrin, endosulfan,enfrin, EPN, ethiofencarb, ethion, ethoate, ethoprop, etrimfos, famphur,fenbutatin-oxide, fenitrothion, fenson, fensulfothion, fenthion,fenvalerate, fonofos, formetanate hydrochloride, formothion, fosthietan,hydroprene, isofenphos, isoxathion, isothioate, malathion, mecarbam,mecarphon, menazon, meobal, mephosfolan, mercaptodimethur,methamidophos, methidathion, methomyl, methoprene, MIPC, mirex,monocrotophos, MTMC, naled, nicotine, omethoate, oxamyl,oxydemeton-methyl, oxydisulfoton, parathion, permethrin, phenthoate,phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb,pirimiphos, plifenate, profenofos, promecarb, propargite, propetamphos,propoxur, prothiophos, prothoate, quinalphos, resmethrin, ronnel,ryania, salithion, schradan, sulfotepp, sulprofos, temephos, TEPP,terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetrasul,thiocyclam-hydrogenoxalate, thiometon, thioquinox, triazophos,trichloronate, trichloron, vamidothion, melvinphos, TEPP, trichlorofon,O,O-dimethyl phosphorochloriodothioate, methyl parathion, demeton O,dicapthon, O,O-diethylphosphorochloridothioate, propham, matacil, m1-ethylpropyl!phenylmethylcarbamate & m1-ethylpropyl!phenylmethylcarbamate (mixture), pyrethrum, benzylthiocyanate, rotenone, eugenol, and mixtures thereof, and in mixturewith other pesticides. Salts and esters of these insecticides also canbe used as the intercalant pesticide.

MISCELLANEOUS PESTICIDES

Aminozide, ancymidol, anthraquinone, brodifacoum, bromadiolone, butoxypolypropylene glycol, carbon tetrachloride, chloflurecol-methyl ester,chlormequat chloride, chlorophacinone, chloropicrin, chlorphonium,chlonitralid, coumachlor, coumafuryl, crimidine, cyoxmetril, deet,diazacosterol hydrochloride, dibutyl phthalate, ethyl hexanediol,dichlofenthion, difenacoum, dikegulac sodium, diphenylamine, ethephone,fenamiphos, fluoroacetamide, glyoxime, gossyplure, heliotropin acetal,kinoprene, maleic hydrazine, mepiquat-chloride, metaldehyde,metamsodium, naphthalene acetamide, 1-naphthaleneacetic acid,nitrapyrin, pyriminal, scillirosid, sesamex, sulfoxide, trifenmorph,triprene, warfarin, and mixtures thereof, and in mixture with otherpesticides. Salts and esters of these pesticides also can be used as theintercalant pesticide.

In accordance with another embodiment of the present invention, theintercalates can be exfoliated, then used as a pesticide or a componentin a pesticide composition, or dispersed in a solvent or carrier toprovide a viscous or thixotropic pesticide composition. In either case,the pesticide composition can include various optional components andadditives commonly employed in pesticide compositions. Such optionalcomponents include fillers, wetting agents, synergists, colorants,dispersants, emulsifiers, anti-caking agents, defoamers, dedustingagents, sequestering agents, coupling agents, water-softening agents,and the like. These optional components, and appropriate amounts, arewell known to those skilled in the art.

The amount of intercalated and/or exfoliated layered material includedin a liquid carrier or solvent to form viscous compositions orthixotropic suitable to deliver the carrier-dissolved orcarrier-dispersed pesticide, can vary widely depending on the intendeduse and desired viscosity of the pesticide composition. For example,relatively high amounts of intercalate, i.e., about 10% to about 30% byweight of the total composition, are used to form solvent gels havingextremely high viscosities, e.g., 5,000 to 5,000,000 centipoise (cps).Extremely high viscosities, however, also can be achieved with arelatively small concentration of intercalates and/or exfoliatesthereof, e.g., 0.1% to 5% by weight, by adjusting the pH of thecomposition to about 0 to about 6 or about 10 to about 14 and/or byheating the composition above room temperature, e.g., in the range ofabout 25° C. to about 200° C., preferably about 75° C. to about 100° C.

In accordance with an important feature of the present invention,compositions of the present invention containing an intercalate and/orexfoliate, and a solvent or carrier, can be manufactured in aconcentrated form, e.g., as a master gel having about 10 to about 90%,preferably about 20 to about 80%, intercalate and/or exfoliatedplatelets of layered material and about 10 to about 90%, preferablyabout 20 to about 80%, carrier or solvent. The master gel can be dilutedand mixed with additional carrier or solvent to reduce the viscosity ofthe composition to a desired level, or to reduce the pesticideconcentration to an efficacious and safe level for application.

Intercalate or platelet particle loadings in the solvent or carrier arewithin the range of about 0.01% to about 40% by weight, preferably about0.05% to about 20%, more preferably about 0.5% to about 10% of the totalweight of the composition to significantly increase the viscosity of thecomposition. In general, the amount of intercalate and/or plateletparticles incorporated into the carrier or solvent is less than about30% by weight of the total composition, and preferably from about 0.01%to about 20% by weight of the composition, more preferably from about0.01% to about 10% by weight of the composition.

The intercalates, and/or exfoliates thereof, are mixed with a carrier orsolvent to produce viscous compositions including one or more pesticidecompounds, such as an insecticide, dissolved or dispersed in the carrieror solvent. In accordance with an important feature of the presentinvention, a wide variety of pesticide compounds can be incorporatedinto a stable composition of the present invention. Such activecompositions include insecticides, herbicides, and fungicides that actupon contact with the insect, plant, or fungus to topically destroy thepest, or are absorbed or ingested by the pest to systemically destroythe pest.

In accordance with another important feature of the present invention, asecond pesticide or an optional component can be solubilized in acomposition of the present invention or can be homogeneously dispersedthroughout the composition as an insoluble, particulate material. Ineither case, pesticide compositions of the present invention areresistant to composition separation and effectively apply the pesticidecompound to the desired area of application. If required for stability,a surfactant can be included in the composition, such as any disclosedin Laughlin et al. U.S. Pat. No. 3,929,678, hereby incorporated byreference. In general, the pesticide compositions of the presentinvention demonstrate essentially no phase separation when the secondpesticide compound and/or optional components are either solubilized ordispersed as an insoluble material in the compositions.

Therefore, in accordance with an important feature of the presentinvention, the stable intercalated pesticide composition can include anyof the generally known pesticides as the second pesticide, often in theform of a finely divided solid. In general, the amount of the secondpesticide compound in the composition can range from 0%, preferablyabout 0.01%, to about 40%, and preferably from 0.1% to about 30%, byweight of the total composition. The amount of surfactant can range from0%, preferably about 0.01%, to about 15% by weight of the totalcomposition.

An optional exfoliation of the intercalated layered material typicallydelaminates at least about 90% by weight of the intercalated material.Exfoliation provides a more viscous composition when the intercalatedpesticide is homogeneously dispersed in a carrier or solvent. Someintercalates require a shear rate that is greater than about 10 sec⁻¹for relatively thorough exfoliation. The upper limit for the shear rateis not critical. In preferred embodiments of the invention, when shearis employed for exfoliation, the shear rate is greater than about 10sec⁻¹ to about 20,000 sec⁻¹, and in more preferred embodiments, theshear rate is about 100 sec⁻¹ to about 10,000 sec⁻¹. Such intercalatesexfoliate naturally or by heating, or by applying pressure, e.g., 0.5 to60 atmospheres above standard atmospheric pressure with or withoutheating.

When shear is employed for exfoliation, any known method for applying ashear to the intercalant/carrier composition can be used. The shearingaction can be provided by any appropriate method, as for example bymechanical means, by thermal shock, by pressure alteration, or byultrasound, all of which are known in the art. In particularly usefulprocedures, the composition is sheared by mechanical means in which theintercalate, with or without the carrier or solvent, is sheared bystirrers, Banbury®-type mixers, Brabender®-type mixers, injectionmolding machines, long continuous mixers, extruders, and similarmechanical means. Another procedure employs thermal shock in whichshearing is achieved by alternatively raising or lowering thetemperature of the composition causing thermal expansions and resultingin internal stresses which cause shear. In still other procedures, shearis achieved by sudden pressure changes in pressure alteration methods,by ultrasonic techniques in which cavitation or resonant vibrationscause portions of the composition to vibrate or to be excited atdifferent phases and thus subjected to shear. These methods of shearingare merely representative of useful methods, and any method known in theart for shearing intercalates may be used.

Shearing can be achieved by introducing the activated layered materialand intercalant pesticide, or mixture thereof, at one end of an extruder(single or double screw) and receiving the sheared material at the otherend of the extruder. The temperature of the layered material/intercalantpesticide composition, the length of the extruder, residence time of thecomposition in the extruder and the design of the extruder (e.g., singlescrew, twin screw, number of flights per unit length, channel depth,flight clearance, mixing zone) are several variables which control theamount of shear to be applied for exfoliation. Alternatively, thelayered material can be activated and intercalated by introducing thelayered material, water, water-soluble polymer, and intercalantpesticide, or a mixture thereof, at one end of the extruder.

Exfoliation is sufficiently thorough to provide at least about 80%,preferably at least about 85%, more preferably at least about 90%, andmost preferably at least about 95% by weight delamination of the layersto form individual platelet particles that can be substantiallyhomogeneously dispersed in the carrier or solvent. As formed by thisprocess, the platelet particles dispersed in the carrier or solvent havethe thickness of the individual layers plus one to five monolayerthicknesses of intercalated pesticide, or small multiples less thanabout 10, preferably less than about 5 and more preferably less thanabout 3 of the layers, and still more preferably 1 or 2 layers. In thepreferred embodiments of this invention, intercalation and delaminationof every interlayer space is complete so that all or substantially allindividual layers delaminate one from the other to form separateplatelet particles for admixture with the carrier or solvent. In oneembodiment, the compositions initially include all intercalated layeredmaterial, completely without exfoliation, to provide relatively lowviscosities for transportation and pumping until it is desired toincrease viscosity via exfoliation. In cases where intercalation betweensome layers is incomplete, those layers do not delaminate in the carrieror solvent, and form platelet particles comprising layers in a coplanaraggregate.

The effect of adding nanoscale, particulate dispersed plateletparticles, derived from the intercalates, into an organic liquidcarrier, typically is an increase in viscosity. Pesticide compositionscomprising a solvent containing a desired loading of platelets obtainedfrom exfoliation of the intercalates and are outstandingly suitable ascommercial products. Such compositions are viscous liquids or gels thatresist leaking from packages and are easy to collect if spilled. Thecompositions according to the invention also are easily dissolved,dispersed or emulsified in an appropriate solvent by pesticideapplicators, who then can apply the correct dosage of pesticide to thedesired surface. Some viscous or gelled pesticide compositions can bepackaged in water-soluble packaging. Such compositions resist leakagefrom the package if the package is damaged. Accordingly, the pesticideapplicator does not come in contact with the pesticide, and accidentalspillage or leakage of the pesticide is essentially eliminated.

The following are specific clay:water-soluble polymer intercalatepreparations to more particularly illustrate the activation of a layeredmaterial and are not to be construed as limitations thereon. Theseclay-polymer intercalates constitute one form of an activated clay, andcan be used as a precursor to adding the intercalant pesticide.Alternatively, water alone or an aqueous solution of a water-miscibleorganic solvent is added to activate the clay prior to adding theintercalant pesticide. In another embodiment, the clay is activated inthe presence of an intercalant pesticide.

Preparation of Clay-PVP Complexes

Materials:

Clay-sodium montmorillonite;

Intercalant polymer-PVP (molecular weights of 10,000 and 40,000).

To prepare clay (sodium montmorillonite)-PVP complexes (i.e.,intercalates), three different processes were used for polymerintercalation to activate the clay:

1. Mixture of a 2% PVP/water solution with a 2% clay/water suspension ina ratio sufficient to provide a polymer concentration of at least about8% by weight, preferably at least about 10% by weight, based on the dryweight of the clay.

2. Dry clay powder (about 8% by weight moisture) was gradually added toa 2% PVP/water solution in a ratio sufficient to provide a polymerconcentration of at least about 8% by weight, preferably at least about10% by weight, based on the dry weight of the clay.

3. Dry PVP was mixed with dry clay, and the resulting mixture washydrated with about 25 to about 50%, preferably about 35% to about 40%by weight water, based on the dry weight of the clay, and then extruded.

Mixtures 1 and 2 were agitated at room temperature for 4 hours. Theclay:PVP weight ratio was varied from 90:10 to 20:80.

The examples in Table 1 show that each method of preparation yielded aclay-PVP complex (intercalate), and that intercalation results do notdepend upon a particular method of preparation (1, 2, or 3) or upon themolecular weight of the intercalant polymer (PVP), but do depend uponthe ratio of clay:PVP. In Table 1, data from x-ray diffraction patternsfor clay-PVP complexes with different ratios of components aresummarized. The plot of this data is illustrated in FIG. 4. From thisdata (Table 1, FIG. 4) the stepwise character of intercalation while thepolymer is being sorbed in the interlayer space between adjacentplatelets of the montmorillonite clay is seen. There are increasingd(001) values from 12 Å (for clay with no sorbed PVP, i.e., FIG. 11) toa 24-25 Å spacing between adjacent clay platelets with sorption of20-30% PVP. FIG. 6 illustrates a d(001) value of 23.62 Å for a PVP:clayweight ratio of 20:80.

The next step to 30-32 Å spacing occurs when the sorbed PVP content isincreased to 40-60%. FIG. 10 illustrates a d(001) value of 31.94 Å for aPVP:clay weight ratio of 50:50. Further increasing the sorbed PVPcontent to 70-80% increases the d(001) values to 40-42 Å. FIG. 12illustrates a d(001) value of 41 Å for a PVP:clay weight ratio of 80:20.There are d(002) values together with d(001) values in x-ray diffractionpatterns of all intercalates obtained (Table 1, FIG. 4). This indicatesthe regularity of clay-PVP intercalate structures.

                  TABLE 1                                                         ______________________________________                                        PVP, %.sup.1     d(001), Å                                                                          d(002), Å                                       ______________________________________                                        1      0.0           12.4     6.2                                             2      10.0          17.5     8.6                                             3      20.0          24.0     11.4                                            4      30.0          25.0     12.0                                            5      40.0          30.0     15.2                                            6      45.0          31.0     15.2                                            7      50.0          30.0     15.5                                            8      55.0          32.0     16.5                                            9      60.0          34.0     17.0                                            10     70.0          40.0     21.0                                            11     80.0          42.0     21.0                                            ______________________________________                                         .sup.1 Percent by weight, based on the dry weight of the clay plus            polymer.                                                                 

Preparation of Clay-PVA Complexes

Materials:

Clay-sodium montmorillonite;

Intercalant polymer-PVA (degree of hydrolysis 75-99%, molecular weight10,000).

To prepare clay (sodium montmorillonite)-PVA complexes (i.e.,intercalates), three different processes were used for polymerintercalation to activate the clay:

1. Mixture of a 2% PVA/water solution with a 2% clay/water suspension ina ratio sufficient to provide a polymer concentration of at least about8% by weight, preferably at least about 10% by weight, based on the dryweight of the clay.

2. Dry clay powder was gradually added to a 2% PVA/water solution in aratio sufficient to provide a polymer concentration of at least about 8%by weight, preferably at least about 10% by weight, based on the weightof the clay.

3. Dry clay was moisturized with PVA/water solution to a moisturecontent of 25% to 80%, preferably about 35% to 40% water, and thenextruded.

The mixtures 1 and 2 were agitated at room temperature for 4 hours.

The weight ratio clay:PVA was varied from 80:20 to 20:80.

Some of the intercalates were studied by x-ray diffraction. Theseexamples show that all methods of preparation yielded the compositeclay-PVA complexes (intercalates), and the results of the intercalationdo not depend upon a particular method of preparation (1, 2, or 3), themolecular weight of the intercalant polymer (PVA), or the degree ofhydrolysis, but do depend on the clay:PVA ratio. In Table 2 data fromx-ray diffraction patterns for clay-PVA complexes with different ratiosof components are summarized. A plot of this data is illustrated in FIG.5. From this data (Table 2, FIG. 5), the stepwise character ofincreasing d(001) values from 12 Å (for clay with no sorbed PVA, i.e.,FIG. 11) to 22-25 Å spacing between adjacent platelets with sorption of20-30% PVA is illustrated. FIG. 8 illustrates a d(001) value of 20.04 Åfor a PVA:clay weight ratio of 20:80. The next step to 30-33 Å occurswhen the sorbed PVA content increases to 35-50%. A further increase ofthe sorbed PVA content to 60-80% increases the d(001) values to 40-45 Å.

Heating the clay-PVA intercalates at 120° C. for 4 hours did notsignificantly change the d(001) values (Table 2, FIG. 5). The change ind(001) value from 12.4 Å to 9.6 Å for the sample containing 0% PVAillustrates that water is expelled from the clay, the spacing betweenclay platelets is decreased.

                  TABLE4 2                                                        ______________________________________                                                                  d(001), Å                                       PVA %.sup.1      d(001), Å                                                                          120° C.                                      ______________________________________                                        1      0.0           12.4     9.6                                             2      10.0          17.0     16.8                                            3      20.0          23.0     22.0                                            4      30.0          25.0     24.0                                            5      35.0          32.0     32.0                                            6      40.0          31.0     30.0                                            7      45.0          33.0     32.0                                            8      50.0          32.0     32.0                                            9      60.0          42.0     42.0                                            10     70.0          44.0     42.0                                            11     80.0          45.0     44.0                                            ______________________________________                                         .sup.1 Percent by weight, based on the dry weight of the clay plus PVA.  

Specifically, FIGS. 6 through 8 are x-ray diffraction patterns of blendsof different water-soluble polymers with sodium bentonite clay. Thepatterns of FIGS. 6 and 7 are taken from clay intercalated with 20% byweight polyvinylpyrrolidone (weight average molecular weight 10,000 forFIG. 6; 40,000 for FIG. 7) and 80% by weight sodium bentonite clay. Theblends were formed by mixing the PVP and clay from a solution of PVP anda 2% dispersion of sodium bentonite in a 1:4 ratio, respectively. Asshown, the PVP: clay complexed since no d (001) smectite peak appears atabout 12.4 Å (i.e., see FIG. 11 for untreated sodium bentonite clay).Similar results are shown for 20% polyvinyl alcohol, 80% sodiumbentonite, as shown in FIG. 8, blended in the same way and in the sameratio. An x-ray diffraction pattern for sodium bentonite containing noadditives is presented FIG. 11 for comparison.

The d(001) peak of nonexfoliated (layered) and untreated sodiumbentonite clay appears at about 12.4 Å, as shown in the x-raydiffraction pattern for sodium bentonite clay (containing about 10% byweight water) in FIG. 11 and in the lower x-ray diffraction patterns ofFIGS. 9 and 10. FIG. 9 includes x-ray diffraction patterns of sodiumbentonite clay (montmorillonite) and a PVP:clay complex that wasobtained by extrusion of a blend of 20% by weight polyvinylpyrrolidone(molecular weight 10,000) and 80% by weight sodium bentonite clay(containing a crystobalite impurity, having a d-spacing of about 4.05 Å)with 35% water based on the weight of dry clay plus polymer. As shown inFIG. 9, the PVP and clay complexed since no d(001) smectite peak appearsat about 12.4 Å. There are basal spacings with a d(001) peak of PVP:claycomplex at about 24 Å and d(002) peak of PVP:clay complex at about 12 Å,that shows close to regular structure of this intercalated compositewith a PVP:clay ratio equal to 1:4.

FIG. 10 contains x-ray diffraction patterns of sodium bentonite clay(montmorillonite) and PVP:clay complex that was obtained by extrusion ofblend of 50% by weight polyvinylpyrrolidone (molecular weight 10,000)and 50% of sodium bentonite clay (containing a crystobalite impurity,having d-spacing of about 4.05 Å) with 35% water based on the weight ofdry clay plus polymer. As shown in FIG. 10, the PVP:clay complexed sinceno d(001) smectite peak appears at about 12.4 Å. There are basalspacings with a d(001) peak of the PVP:clay complex at about 32 Å and ad(002) peak of PVP:clay complex at about 16 Å that shows close toregular structure of this intercalated composite with a PVP:clay ratioequal to 1:1. When mechanical blends of powdered sodium bentonite clay(containing about 10% by weight water) and powdered polyvinylpyrrolidone(PVP) polymer were mixed with water (about 75% by weight water), thepolymer was intercalated between the bentonite clay platelets. Anexothermic reaction occurred that, it is theorized, resulted from thepolymer being sufficiently bonded to the internal faces of the clayplatelets for exfoliation of the intercalated clay.

Treatment of the sodium bentonite with an aqueous solution of thewater-soluble polymer provides an activated clay that subsequently canbe intercalated with an intercalant pesticide, either containing orlacking a polar moiety. It should be noted that exfoliation of anintercalated clay did not occur unless the bentonite clay included waterin an amount of at least about 4% by weight, based on the dry weight ofthe clay. When inter-calating in a phyllosilicate slurry, it has beenfound that at least about 65% by weight water, based on total weight,provides easier mixing and faster migration of the polymer and pesticideinto the spaces between platelets.

It also should be noted that exfoliation can occur without shearing,i.e., the layered clay exfoliated naturally after sufficientintercalation of polymer or pesticide between the platelets of thelayered bentonite, whether the intercalate was prepared using sufficientwater, e.g., at least about 20% by weight, preferably about 30% to about100% by weight, or higher, based on the dry weight of the clay, forsufficient migration of the polymer or pesticide into the interlayerspaces, and preferably also by extruding. Exfoliation should be avoideduntil the intercalant pesticide has contacted the activated clay.

A number of compositions were prepared containing intercalates(complexes) formed by contacting sodium bentonite clay with anactivating composition comprising water and a water-soluble polymer.Sufficient sodium bentonite clay was added to the activating compositionto provide a preferred weight ratio of dry clay/polymer of 4:1 (80% byweight clay/20% by weight polymer) with sufficient water such that theresulting composition contained 35 to 40% by weight water for effectiveextrusion of the composition through die openings of an extruder. Thepolymer and water are mixed with the clay to complex (intercalate) thepolymer between adjacent clay platelets. The resultingpolymer-intercalated clay then was contacted with an intercalantpesticide.

EXAMPLE

In general, a clay-polymer intercalate or an untreated clay arecontacted with a pesticide, in the presence of water, to intercalate thepesticide between layers of the clay. Preferably, a water-misciblesolvent is present in the water. An extrusion step accelerates theprocess of intercalating the pesticide between the clay layers. Apesticide containing a polar moiety can be intercalated into eitheruntreated clay, a clay activated with water, or a clay-polymerintercalate. A pesticide lacking a polar moiety is intercalated into aclay-polymer intercalate. When an intercalant pesticide is added to theactivated clay or the clay-polymer intercalant, the pesticide displacesthe water and optional polymer from the space between adjacent clayplatelets and is intercalated therein.

The following are nonlimiting examples of preparing a clay-pesticideintercalant from untreated clay.

Preparation of Clay-Herbicide Intercalates

Materials:

Clay-sodium montmorillonite;

Herbicide-2,4-dichlorophenoxyacetic acid (2,4-D), butyl ester

To prepare clay (sodium montmorillonite)-2,4-D ester complexes (i.e.,intercalates), three different processes are used for intercalation:

1. Mixture of a 2% 2,4-D butyl ester/water dispersion or emulsion with a2% clay/water suspension in a ratio sufficient to provide a 2,4-D butylester concentration of at least about 8% based on the dry weight of theclay.

2. Dry clay powder (about 8% by weight moisture) is gradually added tothe 2% 2,4-D butyl ester/water dispersion or emulsion in a ratiosufficient to provide a 2,4-D butyl ester concentration of at leastabout 8% based on the dry weight of the clay.

3. 2,4-D butyl ester (technical grade) is mixed with dry clay, themixture is hydrated with 35 to 38% of water, based on the dry weight ofthe clay, and then extruded.

Mixtures 1 and 2 are agitated at room temperature for 4 hours.

The intercalation and exfoliation methods of the present invention yieldclay-2,4-D butyl ester intercalates, and the results of theintercalation do not depend upon a particular method of preparation (1,2, or 3), but do depend on the quantity of organic pesticide compoundsorbed between clay platelets.

EXAMPLE Preparation of Clay-Insecticide Intercalates

Materials:

Clay-sodium montmorillonite;

Insecticide-chlorpyrifos

To prepare clay (sodium montmorillonite)chlorpyriphos complexes (i.e.,intercalates), three different processes are used for pesticideintercalation:

1. Mixture of a 2% chlorpyrifos/water dispersion with a 2% sodiummontmorillonite clay/water suspension in a ratio sufficient to provide achlorpyrifos concentration of at least about 8% based on the dry weightof the clay.

2. Dry clay powder is gradually added to a 2% chloripyrifos/waterdispersion in a ratio sufficient to provide a chlorpyrifos concentrationof at least about 8% based on the dry weight of the sodiummontmorillonite clay.

3. Dry sodium montmorillonite clay is moisturized withchlorpyrifos/water dispersion to 20-80% by weight water, and thenextruded.

The mixtures 1 and 2 are agitated at room temperature for 4 hours. Theintercalation method yields a clay-chlorpyrifos intercalate regardlessof the method of preparation.

In another example, a dispersion or emulsion of 30% by weight2,4-dichlorophenoxy acetic acid (2,4-D) and 70% by weight dicamba isprepared in water, at a concentration of 45% by weight of the 2,4-D anddicamba mixture. Thirty grams of the 2,4-D/dicamba mixture is added to a50 ml (milliliter) beaker, and while this mixture is mixed vigorously,1.5 grams of sodium montmorillonite (i.e., POLARGEL NF from AMCOLInternational Corporation) is added. The weight ratio of clay to (2,4-Ddicamba mixture) is--1.9. The mixture is vigorously mixed and heated for1 hour at 85° C.

The heated mixture is allowed to cool to room temperature and theresulting product is subjected to x-ray diffraction. The x-raydiffraction pattern shows that the 2,4-D/dicamba is intercalated in theclay because the periodicity, or d(001) value, of the clay is increasedfrom 12.4 Å, showing that 2,4-D and dicamba are intercalated betweenadjacent clay platelets.

All methods of the present invention used for intercalation yieldclay-pesticide intercalates, and the results of the intercalation do notdepend upon method of preparation (1, 2, or 3), but do depend on thequantity of pesticide sorbed between clay platelets.

The following are further illustrative and nonlimiting examples of thepresent invention. The following examples illustrate intercalated layermaterials wherein the intercalant pesticide isα,α,α-trifluoro-2-6-dinitro-N,N-dipropyl-p-toludine, having the commonname trifluralin and available from Dow Elanco, Indianapolis, Ind.

    ______________________________________                                        EXAMPLE        #1     #2     #3   #4   #5   #6                                ______________________________________                                        Belle Yellow Clay.sup.1                                                                      200.sup.4          200  500  400                               PDTQ.sup.2 Organo Clay                                                                              200    200                                              IVP (Surface Modified Clay).sup.3                                             Deionized Water                                                                               90                     150- 150-                              (pH 3)                                 170  170                               Deionized Water                    60                                         (normal pH)                                                                   Trifluralin     60    142     86  101  214  171                               PEG.sup.5                          34                                         PEG.sup.6                                                                     PVP.sup.7                                                                     PVA.sup.8                                                                     Solvent         35.sup.9                                                                             50.sup.9                                                                             70.sup.10                                                                               90.sup.9                                                                           43.sup.9                         ______________________________________                                        EXAMPLE        #7a    #7b    #8a  #8b  #9a  #9b                               ______________________________________                                        Belle Yellow Clay.sup.1                                                                      400    200    200            200.sup.4                         PDTQ.sup.2 Organo Clay                                                        IVP (Surface Modified Clay).sup.3 200  200                                    Deionized Water                                                               (pH 3)                                                                        Deionized Water        70    170- 130  130   96                               (normal pH)                  180                                              Trifluralin    300    150    153  120   86  102                               PEG.sup.5                                                                     PEG.sup.6      300    150                                                     PVP.sup.7                     30                                              PVA.sup.8                                    40                               Solvent                       38.sup.9                                                                           24.sup.9                                                                           22.sup.9                                                                           26.sup.11                        ______________________________________                                        EXAMPLE     #10a   #10b   #10c #10d #11a #11b #11c                            ______________________________________                                        Belle Yellow Clay.sup.1                                                                   300    300    200  200  200  200  200                             PDTQ.sup.2 Organo Clay                                                        IVP (Surface Modified                                                         Clay).sup.3                                                                   Deionized Water.sup.4                                                                     110                                                               (pH 3)                                                                        Deionized Water.sup.4                                                                            190-   130-  88   80  100   95                             (normal pH)        210    140                                                 Trifluralin.sup.4                                                                         128    154    102   94  150   70   60                             PEG.sup.5                                                                     PEG.sup.6                           150   50   30                             PVP.sup.7                                                                     PVA.sup.8           60     40   20                                            Solvent      31.sup.11                                                                            39.sup.11                                                                            26.sup.11                                                                          24.sup.11                                                                          20.sup.9                                                                           10.sup.9                                                                           10.sup.9                       ______________________________________                                         .sup.1 an unmodified sodium bentonite clay powder having particles            collected on a 325 mesh sieve (U.S. Sieve or Tyler), i.e., at least 44        microns in diameter;                                                          .sup.2 a sodium bentonite clay surface treated with a quaternary ammonium     compound;                                                                     .sup.3 a sodium bentonite clay surface treated with 20% by weight             polyvinylpyrolidone;                                                          .sup.4 amounts of all ingredients are expressed as grams;                     .sup.5 polyethylene glycol, PLURACOL E4000, available from BASF               Corporation, Parsippany, NJ;                                                  .sup.6 polyethylene glycol, PLURACOL E400, available from BASF                Corporation, Parsippany, NJ;                                                  .sup.7 polyvinylpyrrolidone, PVP K15, available from GAF Chemicals Corp.,     Wayne, NJ;                                                                    .sup.8 polyvinyl alcohol, VINOL 540, available from Air Products and          Chemicals, Inc., Allentown, PA;                                               .sup.9 isopropyl alcohol;                                                     .sup.10 xylene; and                                                           .sup.11 ethylene glycol monobutyl ether.                                 

X-ray diffraction patterns for wet and/or dry intercalated pesticides ofExamples #1 through #11c were taken, and are presented herein as FIGS.13-22. In FIGS. 13-30, the peak at 11.21 Å is attributed to trifluralinthat is in excess or crystallized on the surface of the clay. Theintercalated pesticides of Examples #1-#11c were prepared from activatedclay in accordance with the methods described in the previous examples.In each example, crystallization of trifluralin on the clay wasminimized because crystallized trifluralin is not available forintercalation.

Example 1 and FIGS. 13 and 14 show that 23% trifluralin was intercalatedinto the clay. Attempts to intercalate trifluralin into a quaternaryammonium-treated clay failed in Examples 2 and 3.

In particular, FIG. 13 shows that the intercalated clay has aperiodicity of 18.8 Å, an increase from a periodicity of 12.4 Å foruntreated clay. The wet sample was dried in a vacuum oven (10⁻³ torr) at60° C. for 48-60 hours causing the trifluralin to sublimate from theclay, as illustrated in FIG. 14, i.e., periodicity of 12.37 Å.Importantly, FIG. 14 illustrates that a pesticide can be released fromthe intercalate to perform its intended function.

In preparing the intercalates of Examples #1-#11c, it was found thatwarming the activated clay/trifluralin mixture to about 40° C. to about60° C., without vacuum, and extruding the warm mixture produces a morehomogeneous intercalated product. However, because trifluralinsublimates, heating the mixture above about 60° C. to 65° C. produces aproduct having high amounts of crystalline trifluralin. It is envisionedthat other pesticides, that do not sublimate, can be heated up to about80° C. without adverse effects.

Examples #2 and #8a were prepared using about 40% trifluralin. Eachintercalated product showed significant crystallization of trifluralin.Accordingly, the upper limit for intercalating trifluralin is about 40%,and preferably about 30%. Examples #9a, #9b, #10d, and #11c had verylittle visible trifluralin crystals, showing that 30% by weighttrifluralin can be intercalated into an activated clay. Example #9autilized a clay that was surface treated with polyvinylpyrrolidone,whereas the clay used in Examples #9b, #10d, and #11c had 20% PVA, 10%PVA, and 10% PEG, respectively, intercalated into the clay prior tocontact with the trifluralin. Examples #9b and #10d were extruded twice.X-ray diffraction patterns for Examples #9a, #9b, #10d, and #11c are setforth in FIGS. 15-22.

With respect to FIGS. 15 and 16 and Example #9a, the surface-treatedclay, prior to intercalation has a periodicity of about 23 Å. FIG. 15shows that periodicity increased to 34.9 Å after intercalation oftrifluralin into the clay. FIG. 16 is an x-ray diffraction after dryingthe intercalated clay showing that trifluralin is released from theintercalated clay.

FIGS. 17 and 18 are x-ray diffraction patterns of Example #9b showingtrifluralin is intercalated (i.e., periodicity of 17.38 Å), and afterdrying overnight at 67° C. without a vacuum remains intercalated (i.e.,FIG. 18, periodicity 17.54 Å). FIGS. 19-22 show similar results,including release of the pesticide, for Examples #10d and #11c usingless PVA or using PEG as the intercalant polymer.

EXAMPLE 12a

200 g Belle Yellow clay (powder)

20 g PVA (powder mixed dry in clay)

94 g Trifluralin

115 g Deionized water (normal pH)

No organic solvents were used in Example 12a. The ingredients wereadmixed and heated at about 40° C. to about 60° C. during mixing, andthe resulting mixture was extruded twice. The extruded intercalatedproduct was dried at 29° C. Trifluralin crystallized on the sides of themixing vessel. Small crystals of trifluralin were visible in the finalproduct. The x-ray diffraction patterns of wet and dry samples ofExample 12a are set forth in FIGS. 23 and 24. FIGS. 23 and 24 show thattrifluralin intercalated between platelets of the clay (i.e., FIG. 23,periodicity is 19.03 Å) and is released from the intercalate (i.e., FIG.24, periodicity is 12.63 Å).

EXAMPLE 12b

200 g AEG clay (granular)

20 g PVA (powder mixed dry in clay)

94 g Trifluralin

115 g Deionized water (normal pH)

Granular clay was used in Example 12b. The AEG clay is a granular sodiumbentonite having a majority of the particles (i.e., at least 60% byweight) ranging from 210 to 840 microns in diameter. In particular, amaximum of 20% by weight of the particles are larger than 840 microns indiameter, and a maximum of 20% by weight of the particles are smallerthan 210 microns in diameter. The granular clay absorbed water toactivate the outer portion of the granular, but insufficient water waspresent to completely hydrate the granules. Therefore, the granules didnot absorb the water evenly, causing the granules to clump. Clumping ofthe granules caused the trifluralin to coat the outside of the clumpsand form crystals. Trifluralin crystals were observed in the finishedintercalated pesticide even after two extrusions. The trifluralin,therefore, was not evenly dispersed throughout the clay. The product wasdried at 33° C. The x-ray diffraction patterns of wet and dry samples ofExample 12b are set forth in FIGS. 25 and 26.

The x-ray diffraction patterns show that a minor portion of thetrifluralin was intercalated, i.e., the relatively small peak at 19.51 Åand the large trifluralin peak at 11.21 Å in FIG. 25. A majority of thetrifluralin, therefore, merely surface coated the clay granules. FIG. 26further illustrates that the majority of the trifluralin surface coatedthe granules because the trifluralin sublimed during drying to yieldessentially nonintercalated clay, i.e., periodicity of 12.46. Using anincreased amount of water when using a granular clay would overcome thisdifficulty.

EXAMPLE 12c

200 g Belle Yellow clay (powder)

20 g PVA (powder mixed dry in clay)

94 g Trifluralin

23.5 g isopropyl alcohol

115 g Deionized water (normal pH)

Example 12c used a combination of isopropyl alcohol and PVA to activatethe clay. Example #10D was similar to Example 12c, except in Example#10D only 88 g of water was used and a glycol ether was used instead ofisopropyl alcohol. The intercalated products of Examples #10D and 12Cdiffer in appearance only by color, wherein the pesticide of Example 12cis a darker orange color. The intercalated pesticide of Example 12c wasdried at 38° C. X-ray diffraction patterns of wet and dry samples of theintercalated pesticide of Example 12c are set forth in FIGS. 27 and 28,which illustrate intercalation and release of trifluralin.

Examples 13a-13d illustrate the effect of adding 10%, 20%, 30%, and 40%trifluralin, by weight, to clay.

EXAMPLE 13a

200 g Belle Yellow clay

22.2 g Trifluralin (10%)

88.8 g Deionized water (normal pH) (40% by weight of clay andtrifluralin)

EXAMPLE 13b

200 g Belle Yellow clay

50 g Trifluralin (20%)

87.5 g Deionized water (normal pH) (35% by weight of clay andtrifluralin)

EXAMPLE 13c

200 g Belle Yellow clay

86 g Trifluralin (30%)

100 g Deionized water (normal pH) (35% by weight of clay andtrifluralin)

EXAMPLES 13d

200 g Belle Yellow clay

133.3 g Trifluralin (40%)

100 g Deionized water (normal pH) (30% by weight of clay andtrifluralin).

Examples 13a-13c each were extruded once. Example 13d was extrudedtwice. The trifluralin was easily melted in the absence of solvents, buttended to crystallize quickly. Example 13a was too wet for easyprocessing. X-ray diffraction patterns of wet and dry samples ofExamples 13a-13d are set forth in FIGS. 29 and 30.

FIGS. 29 and 30 show that trifluralin is intercalated and is released.The large peak at 11.26 Å for Example 13d (i.e., 40% trifluralin) inFIG. 29 shows that excess trifluralin is present, and no furthertrifluralin can be intercalated into the clay.

As previously stated, the intercalate containing the intercalantpesticide, after drying, can be pelletized to provide a useful pesticideproduct. Alternatively, the pelletized intercalate can be used as acomposition ingredient, and admixed with other solid ingredients toprovide a solid pesticide composition. Finally, the intercalate, eitheras is or after exfoliation, can be dispersed in an organic liquid, toprovide a viscous or a gelled pesticide composition. The viscosity ofthe composition formed by adding the intercalate or exfoliate thereof isdependent upon intercalate loading, as well as a temperature, pH, andwater content of the composition.

It is preferred that platelet loading in a liquid carrier is less thanabout 10%. Platelet particle loadings within the range of about 0.01% toabout 40% by weight, preferably about 0.05% to about 20%, morepreferably about 0.5% to about 10%, significantly enhances viscosity ofa pesticide composition containing a liquid carrier and a layeredmaterial having an intercalant pesticide incorporated therein. Ingeneral, the amount of platelet particles incorporated into a liquidcarrier, such as a polar solvent, e.g., a glycol or polyol, such asglycerol, is less than about 20% by weight of the mixture, andpreferably from about 0.01% to about 20% by weight of the pesticidecomposition mixture, more preferably from about 0.01% to about 10% byweight of the mixture, and most preferably from about 0.01% to about 5%by weight.

When an organic liquid, or solvent, is added to the intercalate orexfoliate thereof, the mixture is mixed until homogenous, and oftenheated, to form a more viscous gel before cooling to room temperature(i.e., 24° C.) to measure the viscosity (i.e., on a Brookfieldviscometer, spindle #4, unless otherwise noted). Mixing a composition atroom temperature typically results in a viscosity of about 2,000 toabout 3,000 centipoises (cps), wherein heating the composition resultedin viscosities of about 3,500 to about 4,000 centipoises (80° C.) andabout 7,000 to about 8,000 centipoises (100° C.), all viscosities beingmeasured at 24° C. Heating to 145° C., then cooling to room temperature,increased the viscosity to about 200,000 to about 600,000 centipoises.

Various organic liquids can be used to provide a viscous, gelled, orthixotropic composition. Preferably, an organic liquid is added to anintercalate made using an intercalant polymer and/or that is exfoliated.Nonlimiting examples of organic solvents that can be used includemethanol, isopropyl alcohol, propylene glycol, glycerol, 1-propanol,acetone, ethanol, ethylene glycol, and 1,4-butanediol. An emulsifiedcombination of silicone oil and water also provided a gel. The organicliquid can be used alone, in combination with water, or in combinationwith other organic liquids.

By increasing the pH substantially outside the range of about 6 to about10, the viscosity of the composition is increased to provide athixotropic gel of viscosity 1,500,000 centipoises, at 24° C., withoutheating. The pH is adjusted by shearing all components, except an acidor base, in a blender for 3 minutes, then adding the acid or base, andshearing for an additional minute.

Numerous modifications and alternative embodiments of the invention willbe apparent to those skilled in the art in view of the foregoingdescription. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the best mode of carrying out the invention. The details of theprocess may be varied substantially without departing from the spirit ofthe invention, and the exclusive use of all modifications which comewithin the scope of the appended claims is reserved.

What is claimed is:
 1. An intercalate, capable of being exfoliated,comprising a swellable layered material and an intercalant pesticide,formed by contacting the layered material, having adjacent platelets ofsaid layered material, with a composition including a first intercalantselected from the group consisting of water; a water-miscible organicsolvent; an aqueous solution of a water-soluble intercalant polymer; anda mixture thereof to form an intercalated layered material, andcontacting the intercalated layered material with an intercalatingcomposition containing an intercalant pesticide and a pesticide carrierselected from the group consisting of water; a water-miscible organicsolvent; and a mixture thereof, said intercalating composition having apesticide concentration of at least 2% by weight, based on the weight ofpesticide, water and organic solvent in the intercalating composition toform the intercalate by sorption and electrostatic complexing of theintercalant pesticide between adjacent spaced layers of the layeredmaterial, without prior sorption of an onium ion or silane couplingagent, to expand the spacing between a predominance of the adjacentplatelets of the activated layered material to at least about 10 Å, whenmeasured after sorption of the intercalant pesticide and drying to amaximum of 5% by weight water in said intercalate, based on the dryweight of the layered material, said pesticide selected from the groupconsisting of the following, including salts thereof, esters thereof andmixtures thereof:allyl alcohol, anilazine, triadimenol, benomyl,benquinox, bunema, captafol, captan, carbendazim, carboxin, chinosol,chloroneb, chlorothalonil, cycloheximide, dazomet, dicloran,dichlofluanid, dichlone, dimethirimol, dinocap, manzeb, dithianon,dodemorph, dodine, drazoxolon, edinfenphos, fenaminosulf, fenapanil,fentiazon, ferbam, folpet, fongarid, guazatine, hymexazol, iprodione,kasugamycin, maneb, 2-methoxyethylmercurychloride chloro(-2-methoxyethyl) mercury, methylthiophenate, metiram, nabam,neo-asozin, o-phenylphenol, phenylmercury acetate, oxycarboxin, parinol,quintozene, phosethyl, piperalin, polyoxin, procymidone, propineb,propazine, propionic acid, prothiocarb, pyracarbolid, pyrazophos,thiabendazole, thiophanate, thiram, tolylfluanid, triadimefon,tridemorph, triforine, triphenyltin acetate, validamycin A, vinclozolin,vondozeb, zineb, chloranil, ziram, 8-quinolinol, sulfallate, metam,glyodin, 2,6-bis dimethylaminomethyl!cyclohexanone, hexachloroacetone,bromoacetyl bromide, picloram, benalaxyl, blasticidin S, bupirimate,buthiobate, chinomethionate, chlozolinate, cymoxanil, cyproconazole,dithianon, ethirimol, etridazole, fenarimol, fenpiclonil, fenpropidin,fenpropimorph, fentin, flusilazole, flutriafol, flutolanl, fuberidazole,furalaxyl, imazalil, imibenconazole, iprobenphos, isoprothiolane,mancozeb, mepronil, methfuroxam, metsulfovax, myclobutanil, nuarimol,ofurace, oxadixyl, polyoxin B, polyoxin D, prochloraz, procymidone,propiconazole, pyroquilon, quintozene, tebucanazole, tetraconazole,triarimol, tricyclazole, triforine, acifluorfen, alachlor, alanap,alloxydim, ametryn, amitrol, asulam, atrazine, azide, barban, benazolin,benefin, bensulide, bentazone, benthiocarb, benzoylprop, benzthiazuron,bifenox, acetochlor, acrolein, benazolin, buthidazole, allidochlor,bromacil, bromofenoxin, bromoxynil, butachlor, butralin, buturon,butylate, chlometoxynil, chloramben, chlorbromuron, chlorfenprop,chloridazon, chlorotoluron, chloroxuron, chlorpropham, chlorthiamid,2,4,6-trichlorophenyl-4-nitrophenyl ether, crotoxyphos, cycloate,cyprazine, 2,4-dichlorophenoxyacetic acid, dalapon,4-(2,4-dichlorophenoxy) butyric acid, dimethyl tetrachloroterephthalate,a mixture of tris (2,4-dichlorophenoxyethyl) phosphite, and bis(2,4-dichlorophenoxyethyl) phosphite, desmedipham,2-(2,4-dichlorophenoxy)propionic acid, desmetryn, diallate, dicamba,dichlobenil, dichlorprop, diethatyl, difenoxuron, diclofop, dimexano,dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diuron,endothall, erbon, ethofumesate, fenac, fenuron, flamprop, fluchloralin,S-ethyl dipropylthiocarbamate, pentachlorophenol, fluometuron,fluorodifen, flurecol, glyphosate, glyphosine, hexazinone, ioxynil,isopropalin, isoproturon, karbutilate, lenacil, linuron, mecoprop,medinoterb, methazole, methoprotryne, metobromuron, metolachlor,metoxuron, metribuzin, molinate, monalide, monlinuron, monuron,naptalam, neburon, nitralin, nitrofen, norea, norflurazon, oryzalin,oxadiazon, paraquat, pebulate, penoxalin, perfluidone, phenisopham,phenmedipham, picloram, procyazine, profluralin, prometon, prometryn,pronamide, propachlor, propanil, propazine, propham, secbumeton,siduron, silvex, simazine, swep, 2,4,5-trichlorophenoxy acetic acid,2,3,6-trichlorobenzoic acid, tebuthiuron, terbacil, terbumeton,terbuthylazine, terbutol, terbutryn, tetrafluoron, triallate,trietazine, trifluralin, vernolate, 1-naphthaleneacetic acid,N-m-tolylphthalamic acid, ethyl-1-naphthalene acetate, chloroaceticacid, trichloroacetic acid, p-chloromandelic acid,dimethylamino-2,3,5-triiodobenzoate, 2-naphthoxyacetic acid,phenoxyacetic acid, 2-phenoxypropionic acid, o-chlorophenoxy aceticacid, p-chlorophenoxy acetic acid, 4-chloro-2-methyl phenoxyacetic acid,silvex, 4- (4-chloro-o-tolyl)oxy!butyric acid, p-bromophenoxy aceticacid, dimethylamino-4 2,4-dichlorophenoxy!butryate, 3-indolebutyricacid, 3-indoleacetic acid, 3-indolepropionic acid, gibberellic acid,N,N-dimethylsuccinamic acid, 2-furanacrylic acid, endothal,1-naphthaleneacetamide, allidochlor, N-methyl-N-1-naphthylacetamide,N-1-naphthyl acetamide, 2- 3-chlorophenoxy!propionamide, noruron,siduron, metobromuron, terbacil, chloroxuron, aminotriazole, cyanazine,chlorflurenol, chlorsulfuron, cyanazine, cyometrinil,3,6-dichloropicolinic acid, dichlofop, difenzoquat, diphenamid,ethaflualin, ethepon, flurazole, flurenol, fluridone, fosamine, isouron,mefluidide, 1,8-naphthalic anhydride, napropamide, pyrazon, thoibencarb,anilazine, diphenatrile, N- 2,4-dichlorophenoxyl)acetyl-DL-methionine,daminozide, pyrazon, ethoxyquin, propham,S-carboxymethyl-N,N-dimethyldicarbamate, phosphan, merphos, ethephon,tricamba, amiben, glufosinate, indole-3-butyric acid, β-naphthoxyaceticacid, triclopyr, 9-undecylenic acid, oxyflurofen, dinitrocresol,flurtamone, diflufenican, difunon, fomesafen, clethodim, sethoxydim,haloxyfop, tralkoxydim, fenoxaprop, fluazifop, phaseolotoxin,rhizobitoxine, barban, ethephon, tetcyclacis, mepiquat chloride,ancymidol, uniconzaole, paclobutrazol, diquatop, pendimethalin,karbutilate, asulam, clopyralid, fluroxypyr, chlorimuron, chlorsulfuron,metsulfuron, buthidazole, imazamethabenz, imazapyr, imazaquin,imazethapry, isoxaben, cinmethylin, ethofumesate, acephate, aldicarb,aldoxycarb, aldrin, d-trans allethrin, allyxycarb, aminocarb, amitraz,azinphos, azinphos, azocyclotin, azothoate, bendiocarb, benzomate,binapacryl, bomyl, 2-sec-butylphenyl N-methylcarbamate, bromophos,bromophos-ethyl, bromopropylate, butacarb, butocarboxim, chlordane,chlordecone, heptachlor, lindane, methoxychlor, toxaphene,butoxicarboxim, carbaryl, carbofuran, carbophenothion, cartap,chloridimeform, chlorfenethol, chlorfenvinphos, chlormephos,chlorobenzilate, chloropropylate, chlorphoxim, chlorpyrifos,chlorthiophos, coumaphos, 2-chlorophenyl-N-methylcarbamate, crufomate,cryolite, cyanofenphos, cyanophos, cyhexatin, cypermethrin, cythioate,dichloro diphenyl trichloroethane, 2,2-dichlorovinyl o,o-dimethylphosphate, demeton, demeton-S-methyl, dialifor, diazinon, dicofol,dicrotophos, dieldrin, dienochlor, diflubenzuron, dimefox, dimethoate,dimethrin, dinobuton, dioxacarb, dioxathion, disulfoton,2-methyl-4,6-dinitrophenol, d-phenothrin, endosulfan, enfrin, o-ethylo(4-nitrophenyl) phenylphosphonothioate, ethyl p-nitrophenylthionobenzenephosphonate, ethiofencarb, ethion, ethoate, ethoprop,etrimfos, famphur, feributatin-oxide, fenitrothion, fenson,fensulfothion, fenthion, fenvalerate, fonofos, formetanatehydrochloride, formothion, fosthietan, hydroprene, isofenphos,isoxathion, isothioate, malathion, mecarbam, mecarphon, menazon, meobal,mephosfolan, mercaptodimethur, methamidophos, methidathion, methomyl,methoprene, isoprocarb, mirex, monocrotophos, m-tolyl-N-methylcarbamate,naled, nicotine, omethoate, oxamyl, oxydemeton-methyl, oxydisulfoton,parathion, permethrin, phenthoate, phorate, phosalone, phosmet,phosphamidon, phoxim, pirimicarb, pirimiphos, plifenate, profenofos,promecarb, propargite, propetamphos, propoxur, prothiophos, prothoate,quinalphos, resmethrin, ronnel, ryania, salithion, schradan, sulfotepp,sulprofos, temephos, tetraethyl diphosphate, terbufos,tetrachlorvinphos, tetradifon, tetramethrin, tetrasul,thiocyclamhydrogenoxalate, thiometon, thioquinox, triazophos,trichloronate, trichloron, vamidothion, melvinphos, trichlorofon,O,O-dimethyl phosphorochloriodothioate, methyl parathion, demeton O,dicapthon, O,O-diethylphosphorochloridothioate, propham, matacil, amixture of m 1-ethylpropyl!phenylmethylcarbamate and m1-ethylpropyl!phenylmethylcarbamate, pyrethrum, benzyl thiocyanate,rotenone, eugenol, aminozide, ancymidol, anthraquinone, brodifacoum,bromadiolone, butoxy polypropylene glycol, carbon tetrachloride,chloflurecol-methyl ester, chlormequat chloride, chlorophacinone,chloropicrin, chlorphonium, chlonitralid, coumachlor, coumafuryl,crimidine, cyoxmetril, deet, diazacosterol hydrochloride, dibutylphthalate, ethyl hexanediol, dichlofenthion, difenacoum, dikegulacsodium, diphenylamine, ethephone, fenamiphos, fluoroacetamide, glyoxime,gossyplure, heliotropin acetal, kinoprene, maleic hydrazine,metaldehyde, metam-sodium, naphthalene acetamide, 1-naphthaleneaceticacid, nitrapyrin, pyriminal, scillirosid, sesamex, sulfoxide,trifenmorph, triprene, and warfarin, and wherein said intercalantpolymer, when included in the frist intercalant composition, is selectedfrom the following, salts thereof and mixtures thereof:polyvinylpyrrolidone having a repeating structure (I): ##STR13## whereinn is in the range of 2 to about 1500; metal salts ofpolyvinylpyrrolidone; hydrolyzed polyvinylpyrrolidone of structure (II):##STR14## wherein n is in the range of 2 to about 1500; copolymers ofvinylpyrrolidone and a vinyl amide of γ-amine butyric acid; polyvinylalcohol having 5% or less acetyl groups; polyvinyl alcohol having 1% orless acetyl groups; polyacrylic acid polymers; polyacrylic acidcopolymers; partially or fully neutralized salts of polyacrylic acidpolymers and polyacrylic acid copolymers; poly(methacrylic acid);poly(methacrylamide); poly(N,N-dimethylacrylamide);poly(N-isopropylacrylamide); poly(N-acetamidoacrylamide);poly(N-acetmidomethacrylamide); acrylic interpolymers of polyacrylicacid with poly(methacrylic acid), polyacrylic acid withpoly(methacrylamide), and poly-acrylic acid with methacrylic acid,polyvinyloxazolidone; polyvinylmethyloxazolidone;polyoxypropylene-polyoxyethylene block polymers having one of thefollowing structures: ##STR15## wherein x and z are each an integer inthe range of about 4 to about 30, and y is an integer in the range ofabout 4 to about 100; polyacrylamide; copolymers of acrylamide;acrylamide/sodium acrylate copolymers; acrylate/acrylamide copolymers;acrylate/ammonium methacrylate copolymers; acrylate/diacetoneacrylamidecopolymers; acrylic/acrylate copolymers; adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymers; ammoniumacrylate copolymers; ammonium styrene/acrylate copolymers; ammoniumvinyl acetate/acrylate copolymers; aminomethylpropanolacrylate/diacetoneacrylamide copolymers; aminomethylpropanediolacrylate/diacetoneacrylamide copolymers; butyl benzoic acid/phthalicanhydride/trimethylolethane copolymers; cornstarch/acrylamide/sodiumacrylate copolymers; diethylene glycolamine/epichlorohydrin/piperazinecopolymers; dodecanedioic acid/cetearyl alcohol/glycol copolymers;ethylene/vinyl alcohol copolymers; ethyl esters of polyethylenimines;isopropyl ester of methyl vinyl ether/maleic anhydride copolymers;melamine/formaldehyde resin; methacryloyl ethyl betaine/methacrylatecopolymers; methoxyethylene glycol/dodecyl glycol copolymers;octadecene/maleic anhydride copolymers;octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers;octylacrylamide/acrylate copolymers; polyethylene glycol/dodecyl glycolcopolymers; polyethyleneimine; phthalic anhydride/glycerin/glycidyldecanoate copolymers; metal salts of acrylic and polyacrylic acid;polyaminopropyl biguanide; polymeric quaternary ammonium salts;polyvinyl imidazolinium acetate; potassium polyacrylate; sodiumpolyacrylate; metal salts of methyl vinyl ether/maleic anhydridecopolymers; vinylpyrrolidone/eicosene copolymers; vinylpyrrolidone/ethylmethacrylate/methacrylic acid copolymers; vinylpyrrolidone/hexadecenecopolymers; vinylpyrrolidone/vinyl acetate copolymers;polyvinylpyrrolidone/vinyl acetate/itaconic acid copolymers; sodiumacrylate/vinyl alcohol copolymers; C₄ -C₁₂ metal salts of olefin/maleicacid copolymers; sodium polymethacrylate; sodium polystyrene sulfonate;sodium styrene/acrylate/polyethylene glycol-10 dimaleate copolymers;water-soluble esters and ethers of cellulose; sodiumstyrene/polyethylene glycol-10 maleate/nonoxynol-10 maleate/acrylatecopolymers; starch/acrylate/acrylamide copolymers; styrene/acrylamidecopolymers; styrene/acrylate/ammonium methacrylate copolymers;styrene/maleic anhydride copolymers; styrene/polyvinyloxazolidonecopolymers; sucrose benzoate/sucrose acetate isobutyrate/butyl benzylphthalate copolymers; sucrose benzoate/sucrose acetate isobutyrate/butylbenzylphthalate/methyl methacrylate copolymers; urea formaldehydepolymers; urea/melamine/formaldehyde polymers; vinyl acetate/crotonicacid copolymers; vinyl alcohol copolymers; and polysaccharides.
 2. Apesticide composition comprising the intercalate of claim 1, in aconcentration of about 0.05% to about 99.5% by weight, and an inertcarrier.
 3. The pesticide composition of claim 2 wherein the inertcarrier is a solid selected from the group consisting of calcined clay,ground corn cobs, sawdust, silica, wood chips, sand, and mixturesthereof.
 4. A pesticide composition comprising an intercalate, togetherwith an organic solvent, said intercalate formed by contacting a layeredmaterial, having a moisture content of at least about 4% by weight, witha composition comprising an aqueous solution of an intercalant polymer,said intercalant polymer having a concentration of at least 2% by weightbased on the total weight of water and intercalant polymer in saidcomposition, to form a polymer intercalated layered material by sorptionand complexing of the intercalant polymer between adjacent spaced layersof the layered material to expand the spacing between a predominance ofthe adjacent platelets of said layered material to at least about 10 Å,when measured after sorption of the intercalant polymer and drying to amaximum of 5% by weight water, based on the dry weight of the layeredmaterial; and then contacting the polymer intercalated layered materialwith an intercalating composition comprising an intercalant pesticideand a carrier for said intercalant pesticide to provide the intercalate,wherein the intercalant pesticide is sorbed and electrostaticallycomplexed between adjacent spaced layers of the layered material, saidpesticide selected from the group consisting of the following, includingsalts thereof, esters thereof and mixtures thereof:allyl alcohol,anilazine, triadimenol, benomyl, benquinox, bunema, captafol, captan,carbendazim, carboxin, chinosol, chloroneb, chlorothalonil,cycloheximide, dazomet, dicloran, dichlofluanid, dichlone, dimethirimol,dinocap, manzeb, dithianon, dodemorph, dodine, drazoxolon, edinfenphos,fenaminosulf, fenapanil, fentiazon, ferbam, folpet, fongarid, guazatine,hymexazol, iprodione, kasugamycin, maneb, 2-methoxyethylmercurychloridechloro(-2-methoxyethyl) mercury, methylthiophenate, metiram, nabam,neo-asozin, o-phenylphenol, phenylmercury acetate, oxycarboxin, parinol,quintozene, phosethyl, piperalin, polyoxin, procymidone, propineb,propazine, propionic acid, prothiocarb, pyracarbolid, pyrazophos,thiabendazole, thiophanate, thiram, tolylfluanid, triadimefon,tridemorph, triforine, triphenyltin acetate, validamycin A, vinclozolin,vondozeb, zineb, chloranil, ziram, 8-quinolinol, sulfallate, metam,glyodin, 2,6-bis dimethylaminomethyl!cyclohexanone, hexachloroacetone,bromoacetyl bromide, picloram, benalaxyl, blasticidin S, bupirimate,buthiobate, chinomethionate, chlozolinate, cymoxanil, cyproconazole,dithianon, ethirimol, etridazole, fenarimol, fenpiclonil, fenpropidin,fenpropimorph, fentin, flusilazole, flutriafol, flutolanl, fuberidazole,furalaxyl, imazalil, imibenconazole, iprobenphos, isoprothiolane,mancozeb, mepronil, methfuroxam, metsulfovax, myclobutanil, nuarimol,ofurace, oxadixyl, polyoxin B, polyoxin D, prochloraz, procymidone,propiconazole, pyroquilon, quintozene, tebucanazole, tetraconazole,triarimol, tricyclazole, triforine, acifluorfen, alachlor, alanap,alloxydim, ametryn, amitrol, asulam, atrazine, azide, barban, benazolin,benefin, bensulide, bentazone, benthiocarb, benzoylprop, benzthiazuron,bifenox, acetochlor, acrolein, benazolin, buthidazole, allidochlor,bromacil, bromofenoxin, bromoxynil, butachlor, butralin, buturon,burylate, chlometoxynil, chloramben, chlorbromuron, chlorfenprop,chloridazon, chlorotoluron, chloroxuron, chlorpropham, chlorthiamid,2,4,6-trichlorophenyl-4-nitrophenyl ether, crotoxyphos, cycloate,cyprazine, 2,4-dichlorophenoxyacetic acid, dalapon,4-(2,4-dichlorophenoxy) butyric acid, dimethyl tetrachloroterephthalate,a mixture of tris (2,4-dichlorophenoxyethyl) phosphite, and bisdichlorophenoxyethyl) phosphite, desmedipham,2-(2,4-dichlorophenoxy)propionic acid, desmetryn, diallate, dicamba,dichlobenil, dichlorprop, diethatyl, difenoxuron, diclofop, dimexano,dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diuron,endothall, erbon, ethofumesate, fenac, fenuron, flamprop, fluchloralin,S-ethyl dipropylthiocarbamate, pentachlorophenol, fluometuron,fluorodifen, flurecol, glyphosate, glyphosine, hexazinone, ioxynil,isopropalin, isoproturon, karbutilate, lenacil, linuron, mecoprop,medinoterb, methazole, methoprotryne, metobromuron, metolachlor,metoxuron, metribuzin, molinate, monalide, monlinuron, monuron,naptalam, neburon, nitralin, nitrofen, norea, norflurazon, oryzalin,oxadiazon, paraquat, pebulate, penoxalin, perfluidone, phenisopham,phenmedipham, picloram, procyazine, profluralin, prometon, prometryn,pronamide, propachlor, propanil, propazine, propham, secbumeton,siduron, silvex, simazine, swep, 2,4,5-trichlorophenoxy acetic acid,2,3,6-trichlorobenzoic acid, tebuthiuron, terbacil, terbumeton,terbuthylazine, terbutol, terbutryn, tetrafluoron, triallate,trietazine, trifluralin, vernolate, 1-naphthaleneacetic acid,N-m-tolylphthalamic acid, ethyl-1-naphthalene acetate, chloroaceticacid, trichloroacetic acid, p-chloromandelic acid,dimethylamino-2,3,5-triiodobenzoate, 2-naphthoxyacetic acid,phenoxyacetic acid, 2-phenoxypropionic acid, o-chlorophenoxy aceticacid, p-chlorophenoxy acetic acid, 4-chloro-2-methyl phenoxyacetic acid,silvex, 4- (4-chloro-o-tolyl)oxy!butyric acid, p-bromophenoxy aceticacid, dimethylamino-4 2,4-dichlorophenoxy!butryate, 3-indolebutyricacid, 3-indoleacetic acid, 3-indolepropionic acid, gibberellic acid,N,N-dimethylsuccinamic acid, 2-furanacrylic acid, endothal,1-naphthaleneacetamide, allidochlor, N-methyl-N-1-naphthylacetamide,N-1-naphthyl acetamide, 2- 3-chlorophenoxy!propionamide, noruron,siduron, metobromuron, terbacil, chloroxuron, aminotriazole, cyanazine,chlorflurenol, chlorsulfuron, cyanazine, cyometrinil,3,6-dichloropicolinic acid, dichlofop, difenzoquat, diphenamid,ethaflualin, ethepon, flurazole, flurenol, fluridone, fosamine, isouron,mefluidide, 1,8-naphthalic anhydride, napropamide, pyrazon, thoibencarb,anilazine, diphenatrile, N- 2,4-dichlorophenoxyl)acetyl-DL-methionine,daminozide, pyrazon, ethoxyquin, propham,S-carboxymethyl-N,N-dimethyldicarbamate, phosphan, merphos, ethephon,tricamba, amiben, glufosinate, indole-3-butyric acid, β-naphthoxyaceticacid, triclopyr, 9-undecylenic acid, oxyflurofen, dinitrocresol,flurtamone, diflufenican, difunon, fomesafen, clethodim, sethoxydim,haloxyfop, tralkoxydim, fenoxaprop, fluazifop, phaseolotoxin,rhizobitoxine, barban, ethephon, tetcyclacis, mepiquat chloride,ancymidol, uniconzaole, paclobutrazol, diquatop, pendimethalin,karbutilate, asulam, clopyralid, fluroxypyr, chlorimuron, chlorsulfuron,metsulfuron, buthidazole, imazamethabenz, imazapyr, imazaquin,imazethapry, isoxaben, cinmethylin, ethofumesate, acephate, aldicarb,aldoxycarb, aldrin, d-trans allethrin, allyxycarb, aminocarb, amitraz,azinphos, azinphos, azocyclotin, azothoate, bendiocarb, benzomate,binapacryl, bomyl, 2-sec-butylphenyl N-methylcarbamate, bromophos,bromophos-ethyl, bromopropylate, butacarb, butocarboxim, chlordane,chlordecone, heptachlor, lindane, methoxychlor, toxaphene,butoxicarboxim, carbaryl, carbofuran, carbophenothion, cartap,chloridimeform, chlorfenethol, chlorfenvinphos, chlormephos,chlorobenzilate, chloropropylate, chlorphoxim, chlorpyrifos,chlorthiophos, coumaphos, 2-chlorophenyl-N-methylcarbamate, crufomate,cryolite, cyanofenphos, cyanophos, cyhexatin, cypermethrin, cythioate,dichloro diphenyl trichloroethane, 2,2-dichlorovinyl o,o-dimethylphosphate, demeton, demeton-S-methyl, dialifor, diazinon, dicofol,dicrotophos, dieldrin, dienochlor, diflubenzuron, dimefox, dimethoate,dimethrin, dinobuton, dioxacarb, dioxathion, disulfoton,2-methyl-4,6-dinitrophenol, d-phenothrin, endosulfan, enfrin, o-ethylo(4-nitrophenyl) phenylphosphonothioate, ethyl p-nitrophenylthionobenzenephosphonate, ethiofencarb, ethion, ethoate, ethoprop,etrimfos, famphur, fenbutatin-oxide, fenitrothion, fenson,fensulfothion, fenthion, fenvalerate, fonofos, formetanatehydrochloride, formothion, fosthietan, hydroprene, isofenphos,isoxathion, isothioate, malathion, mecarbam, mecarphon, menazon, meobal,mephosfolan, mercaptodimethur, methamidophos, methidathion, methomyl,methoprene, isoprocarb, mirex, monocrotophos, m-tolyl-N-methylcarbamate,naled, nicotine, omethoate, oxamyl, oxydemeton-methyl, oxydisulfoton,parathion, permethrin, phenthoate, phorate, phosalone, phosmet,phosphamidon, phoxim, pirimicarb, pirimiphos, plifenate, profenofos,promecarb, propargite, propetamphos, propoxur, prothiophos, prothoate,quinalphos, resmethrin, ronnel, ryania, salithion, schradan, sulfotepp,sulprofos, temephos, tetraethyl diphosphate, terbufos,tetrachlorvinphos, tetradifon, tetramethrin, tetrasul,thiocyclamhydrogenoxalate, thiometon, thioquinox, triazophos,trichloronate, trichloron, vamidothion, melvinphos, trichlorofon,O,O-dimethyl phosphorochloriodothioate, methyl parathion, demeton O,dicapthon, O,O-diethylphosphorochloridothioate, propham, matacil, amixture of m 1-ethylpropyl!phenylmethylcarbamate and m1-ethylpropyl!phenylmethylcarbarnate, pyrethrum, benzyl thiocyanate,rotenone, eugenol, aminozide, ancymidol, anthraquinone, brodifacoum,bromadiolone, butoxy polypropylene glycol, carbon tetrachloride,chloflurecolmethyl ester, chlormequat chloride, chlorophacinone,chloropicrin, chlorphonium, chlonitralid, coumachlor, coumafuryl,crimidine, cyoxmetril, deet, diazacosterol hydrochloride, dibutylphthalate, ethyl hexanediol, dichlofenthion, difenacoum, dikegulacsodium, diphenylamine, ethephone, fenamiphos, fluoroacetamide, glyoxime,gossyplure, heliotropin acetal, kinoprene, maleic hydrazine,metaldehyde, metam-sodium, naphthalene acetamide, 1-naphthaleneaceticacid, nitrapyrin, pyriminal, scillirosid, sesamex, sulfoxide,trifenmorph, triprene, and warfarin; and wherein said intercalantpolymer is selected from the group consisting of the following, saltsthereof and mixtures thereof: polyvinylpyrrolidone having a repeatingstructure (I): ##STR16## wherein n is in the range of 2 to about 1500;metal salts of polyvinylpyrrolidone; hydrolyzed polyvinylpyrrolidone ofstructure (II): ##STR17## wherein n is in the range of 2 to about 1500;copolymers of vinylpyrrolidone and a vinyl amide of γ-amine butyricacid; polyvinyl alcohol having 5% or less acetyl groups; polyvinylalcohol having 1% or less acetyl groups; polyacrylic acid polymers;polyacrylic acid copolymers; partially or fully neutralized salts ofpolyacrylic acid polymers and polyacrylic acid copolymers;poly(methacrylic acid); poly(methacrylamide); poly(N,N-dimethylacrylamide); poly(N-isopropylacrylamide);poly(N-acetamidoacrylamide); poly(N-acetmidomethacrylamide); acrylicinterpolymers of polyacrylic acid with poly(methacrylic acid),polyacrylic acid with poly(methacrylamide), and poly-acrylic acid withmethacrylic acid, polyvinyloxazolidone; polyvinylmethyloxazolidone;polyoxypropylene-polyoxyethylene block polymers having one of thefollowing structures: ##STR18## wherein x and z are each an integer inthe range of about 4 to about 30, and y is an integer in the range ofabout 4 to about 100; polyacrylamide; copolymers of acrylamide;acrylamide/sodium acrylate copolymers; acrylate/acrylamide copolymers;acrylate/ammonium methacrylate copolymers; acrylate/diacetoneacrylamidecopolymers; acrylic/acrylate copolymers; adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymers; ammoniumacrylate copolymers; ammonium styrene/acrylate copolymers; ammoniumvinyl acetate/acrylate copolymers; aminomethylpropanolacrylate/diacetoneacrylamide copolymers; aminomethylpropanediolacrylate/diacetoneacrylamide copolymers; butyl benzoic acid/phthalicanhydride/trimethylolethane copolymers; cornstarch/acrylamide/sodiumacrylate copolymers; diethylene glycolamine/epichlorohydrin/piperazinecopolymers; dodecanedioic acid/cetearyl alcohol/glycol copolymers;ethylene/vinyl alcohol copolymers; ethyl esters of polyethylenimines;isopropyl ester of methyl vinyl ether/maleic anhydride copolymers;melamine/formaldehyde resin; methacryloyl ethyl betaine/methacrylatecopolymers; methoxyethylene glycol/dodecyl glycol copolymers;octadecene/maleic anhydride copolymers;octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers;octylacrylamide/acrylate copolymers; polyethylene glycol/dodecyl glycolcopolymers; polyethyleneimine; phthalic anhydride/glycerin/glycidyldecanoate copolymers; metal salts of acrylic and polyacrylic acid;polyaminopropyl biguanide; polymeric quaternary ammonium salts;polyvinyl imidazolinium acetate; potassium polyacrylate; sodiumpolyacrylate; metal salts of methyl vinyl ether/maleic anhydridecopolymers; vinylpyrrolidone/eicosene copolymers; vinylpyrrolidone/ethylmethacrylate/methacrylic acid copolymers; vinylpyrrolidone/hexadecenecopolymers; vinylpyrrolidone/vinyl acetate copolymers;polyvinylpyrrolidone/vinyl acetate/itaconic acid copolymers; sodiumacrylate/vinyl alcohol copolymers; C₄ -C₁₂ metal salts of olefin/maleicacid copolymers; sodium polymethacrylate; sodium polystyrene sulfonate;sodium styrene/acrylate/polyethylene glycol-10 dimaleate copolymers;water-soluble esters and ethers of cellulose; sodiumstyrene/polyethylene glycol-10 maleate/nonoxynol-10 maleate/acrylatecopolymers; starch/acrylate/acrylamide copolymers; styrene/acrylamidecopolymers; styrene/acrylate/ammonium methacrylate copolymers;styrene/maleic anhydride copolymers; styrene/polyvinyloxazolidonecopolymers; sucrose benzoate/sucrose acetate isobutyrate/butyl benzylphthalate copolymers; sucrose benzoate/sucrose acetate isobutyrate/butylbenzylphthalate/methyl methacrylate copolymers; urea formaldehydepolymers; urea/melamine/formaldehyde polymers; vinyl acetate/crotonicacid copolymers; vinyl alcohol copolymers; and polysaccharides.
 5. Theintercalate of claim 1 wherein the first intercalant comprises water. 6.The intercalate of claim 5 wherein the first intercalant comprises waterand an organic solvent.
 7. The intercalate of claim 1 wherein the firstintercalant is an aqueous solution of a water-soluble intercalantpolymer.
 8. The intercalate of claim 1 wherein the concentration ofintercalant pesticide is about 0.01% to about 40% by weight, based onthe dry weight of the layered material.
 9. The intercalate of claim 8wherein the concentration of intercalant pesticide is about 0.1% toabout 35% by weight, based on the dry weight of the layered material.10. The intercalate of claim 9 wherein the concentration of intercalantpesticide is about 5% to about 30% by weight, based on the dry weight ofthe layered material.
 11. The intercalate of claim 1 wherein theconcentration of intercalant pesticide is at least about 8% by weight,based on the dry weight of the layered material.
 12. The intercalate ofclaim 7 wherein the concentration of the intercalant polymer is at leastabout 16% by weight, based on the dry weight of the layered material, toachieve spacing between adjacent platelets of said activated layeredmaterial of at least about 10 Å.
 13. The intercalate of claim 7 whereinthe concentration of the intercalant polymer is at least about 35% byweight, based on the dry weight of the layered material, to achievespacing between adjacent platelets of said activated layered material ofat least about 20 Å.
 14. The intercalate of claim 7 wherein theconcentration of the intercalant polymer is at least about 55% byweight, based on the dry weight of the layered material, to achievespacing between adjacent platelets of said activated layered material ofat least about 30 Å.
 15. The intercalate of claim 1 wherein theintercalant pesticide contains at least one polar moiety.
 16. Theintercalate of claim 6 wherein the intercalant pesticide lacks a polarmoiety.
 17. The intercalate of claim 15 wherein the polar moiety isselected from the group consisting of a carboxylic acid, a salt of acarboxylic acid, an ester, an amide, an anhydride, a ketone, analdehyde, cyano, nitro, thiocarbamate, amino, carbamic, phosphate,thiophosphate, sulfoxide, carboximide, urea, sulfone, phosphorothioate,phosphorodithioate, thiourea, dithiocarbamate, phosphoramidodithioate,methylsulfonyl, phosphonate, sulfamide, phosphoramide, sulfonate,dithiocarbonate, hydroxyl, sulfate, sulfinate, sulfamate, andphosphinate.
 18. The intercalate of claim 15 wherein the polar moietyhas two adjacent atoms that are covalently bonded, and the two atomshave a difference in electronegativity of at least about 0.5electronegativity units.
 19. The intercalate of claim 1 wherein thepesticide is selected from the group consisting of fungicides,insecticides, herbicides, acaricides, nematocides, rodenticides,miticides, repellents, growth regulators, larvacides, and mixturesthereof.
 20. The intercalate of claim 1 wherein the pesticide comprisesan herbicide.
 21. The intercalate of claim 20 wherein the herbicide isselected from the group consisting of trifluralin,2,4-dichlorophenoxyacetic acid, dicamba, and mixtures thereof.
 22. Theintercalate of claim 1 wherein the pesticide comprises an insecticide.23. The intercalate of claim 22 wherein the insecticide is chlorpyrifos.24. The intercalate of claim 7 wherein the weight ratio of intercalantpolymer to layered material is at least 1:20.
 25. The intercalate ofclaim 7 wherein the weight ratio of intercalant polymer to layeredmaterial is at least 1:4.
 26. The intercalate of claim 1 wherein theweight ratio of intercalant pesticide to layered material is at leastabout 1:2.
 27. The intercalate of claim 7 wherein the concentration ofintercalant polymer is at least about 0.1% by weight, based on theweight of water and intercalant polymer.
 28. The intercalate of claim 27wherein the concentration of intercalant polymer is at least about 2% byweight.
 29. The intercalate of claim 7 wherein the concentration ofintercalant polymer in said intercalate is at least about 2% by weight,based on the dry weight of layered material, and wherein saidintercalant polymer has a functionality selected from the groupconsisting of an aromatic ring, a carboxyl, a hydroxyl, a carbonyl, anether, an ester, an amine, an amide, an SOx, a POx, wherein x=2, 3, or4, and mixtures thereof.
 30. The intercalate of claim 7 wherein theintercalant polymer is selected from the group consisting ofpolyvinylpyrrolidone, poly(vinyl alcohol), polyvinylimine, polyacrylicacid, poly(methacrylic acid), poly(methacrylamide),poly(N,N-dimethylacrylamide), poly(N-acetamideacrylamide),poly(N-acetomethamido-acrylamide), polyvinyloxazolidone,polyvinylmethyloxazolidone, poly-oxyethylene-polyoxypropylene blockcopolymers, polyethylenimine, and copolymers and mixtures thereof. 31.The intercalate of claim 30 wherein the intercalant polymer is polyvinylalcohol.
 32. The intercalate of claim 30 wherein the intercalant polymeris polyvinylpyrrolidone.
 33. The intercalate of claim 30 wherein theintercalant polymer has a weight average molecular weight in the rangeof about 100 to about 100,000.
 34. The intercalate of claim 1 whereinthe concentration of intercalant pesticide in the intercalatingcomposition is at least about 5% by weight, based on the dry weight ofthe layered material.
 35. The intercalate of claim 34 wherein theconcentration of intercalant pesticide in the intercalating compositionis at least about 30% by weight, based on the dry weight of the layeredmaterial.
 36. A pesticide composition comprising an organic liquidcarrier in an amount of about to about 99.95% by weight of thecomposition, and about 0.05% to about 60% by weight of an intercalatedphyllosilicate material, said intercalated phyllosilicate materialformed by contacting a phyllosilicate, having adjacent phyllosilicateplatelets, with a composition selected from the group consisting ofwater; a water-soluble intercalant polymer; a water-miscible organicsolvent; and a mixture thereof, to form an intercalated phyllosilicate,and contacting the intercalated phyllosilicate with an intercalatingcomposition, without prior sorption of an onium ion or silane couplingagent, comprising a pesticide and a pesticide carrier selected from thegroup consisting of water; a water-miscible organic solvent; and amixture thereof, said intercalating composition having an intercalantpesticide concentration of at least 2% based on the weight of pesticide,water and organic solvent to achieve sorption of the intercalantpesticide between adjacent spaced layers of the phyllosilicatesufficient to expand the spacing between a predominance of the adjacentphyllosilicate platelets to at least about 10 Å, when measured aftersorption of the intercalant pesticide and at a maximum water content ofabout 5% by weight, based on the dry weight of the phyllosilicate, saidpesticide selected from the group consisting of the following, includingsalts thereof, esters thereof and mixtures thereof:allyl alcohol,anilazine, triadimenol, benomyl, benquinox, bunema, captafol, captan,carbendazim, carboxin, chinosol, chloroneb, chlorothalonil,cycloheximide, dazomet, dicloran, dichlofluanid, dichlone, dimethirimol,dinocap, manzeb, dithianon, dodemorph, dodine, drazoxolon, edinfenphos,fenaminosulf, fenapanil, fentiazon, ferbam, folpet, fongarid, guazatine,hymexazol, iprodione, kasugamycin, maneb, 2-methoxyethylmercurychloridechloro(-2-methoxyethyl) mercury, methylthiophenate, metiram, nabam,neo-asozin, o-phenylphenol, phenylmercury acetate, oxycarboxin, parinol,quintozene, phosethyl, piperalin, polyoxin, procymidone, propineb,propazine, propionic acid, prothiocarb, pyracarbolid, pyrazophos,thiabendazole, thiophanate, thiram, tolylfluanid, triadimefon,tridemorph, triforine, triphenyltin acetate, validamycin A, vinclozolin,vondozeb, zineb, chloranil, ziram, 8-quinolinol, sulfallate, metam,glyodin, 2,6-bis dimethylaminomethyl!cyclohexanone, hexachloroacetone,bromoacetyl bromide, picloram, benalaxyl, blasticidin S, bupirimate,buthiobate, chinomethionate, chlozolinate, cymoxanil, cyproconazole,dithianon, ethirimol, etridazole, fenarimol, fenpiclonil, fenpropidin,fenpropimorph, fentin, flusilazole, flutriafol, flutolanl, fuberidazole,furalaxyl, imazalil, imibenconazole, iprobenphos, isoprothiolane,mancozeb, mepronil, methfuroxam, metsulfovax, myclobutanil, nuarimol,ofurace, oxadixyl, polyoxin B, polyoxin D, prochloraz, procymidone,propiconazole, pyroquilon, quintozene, tebucanazole, tetraconazole,triarimol, tricyclazole, triforine, acifluorfen, alachlor, alanap,alloxydim, ametryn, amitrol, asulam, atrazine, azide, barban, benazolin,benefin, bensulide, bentazone, benthiocarb, benzoylprop, benzthiazuron,bifenox, acetochlor, acrolein, benazolin, buthidazole, allidochlor,bromacil, bromofenoxin, bromoxynil, butachlor, butralin, buturon,burylate, chlometoxynil, chloramben, chlorbromuron, chlorfenprop,chloridazon, chlorotoluron, chloroxuron, chlorpropham, chlorthiamid,2,4,6-trichlorophenyl-4-nitrophenyl ether, crotoxyphos, cycloate,cyprazine, 2,4-dichlorophenoxyacetic acid, dalapon,4-(2,4-dichlorophenoxy) butyric acid, dimethyl tetrachloroterephthalate,a mixture of tris (2,4-dichlorophenoxyethyl) phosphite, and bis(2,4-dichlorophenoxyethyl) phosphite, desmedipham,2-(2,4-dichlorophenoxy)propionic acid, desmetryn, diallate, dicamba,dichlobenil, dichlorprop, diethatyl, difenoxuron, diclofop, dimexano,dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diuron,endothall, erbon, ethofumesate, fenac, fenuron, flamprop, fluchloralin,S-ethyl dipropylthiocarbamate, pentachlorophenol, fluometuron,fluorodifen, flurecol, glyphosate, glyphosine, hexazinone, ioxynil,isopropalin, isoproturon, karbutilate, lenacil, linuron, mecoprop,medinoterb, methazole, methoprotryne, metobromuron, metolachlor,metoxuron, metribuzin, molinate, monalide, monlinuron, monuron,naptalam, neburon, nitralin, nitrofen, norea, norflurazon, oryzalin,oxadiazon, paraquat, pebulate, penoxalin, perfluidone, phenisopham,phenmedipham, picloram, procyazine, profluralin, prometon, prometryn,pronamide, propachlor, propanil, propazine, propham, secbumeton,siduron, silvex, simazine, swep, 2,4,5-trichlorophenoxy acetic acid,2,3,6-trichlorobenzoic acid, tebuthiuron, terbacil, terbumeton,terbuthylazine, terbutol, terbutryn, tetrafluoron, triallate,trietazine, trifluralin, vernolate, 1-naphthaleneacetic acid,N-m-tolylphthalamic acid, ethyl-1-naphthalene acetate, chloroaceticacid, trichloroacetic acid, p-chloromandelic acid,dimethylamino-2,3,5-triiodobenzoate, 2-naphthoxyacetic acid,phenoxyacetic acid, 2-phenoxypropionic acid, o-chlorophenoxy aceticacid, p-chlorophenoxy acetic acid, 4-chloro-2-methyl phenoxyacetic acid,silvex, 4- (4-chloro-o-tolyl)oxy!butyric acid, p-bromophenoxy aceticacid, dimethylamino-4 2,4-dichlorophenoxy!butryate, 3-indolebutyricacid, 3-indoleacetic acid, 3-indolepropionic acid, gibberellic acid,N,N-dimethylsuccinamic acid, 2-furanacrylic acid, endothal,1-naphthaleneacetamide, allidochlor, N-methyl-N-1-naphthylacetamide,N-1-naphthyl acetamide, 2- 3-chlorophenoxy!propionamide, noruron,siduron, metobromuron, terbacil, chloroxuron, aminotriazole, cyanazine,chlorflurenol, chlorsulfuron, cyanazine, cyometrinil,3,6-dichloropicolinic acid, dichlofop, difenzoquat, diphenamid,ethaflualin, ethepon, flurazole, flurenol, fluridone, fosamine, isouron,mefluidide, 1,8-naphthalic anhydride, napropamide, pyrazon, thoibencarb,anilazine, diphenatrile, N- 2,4-dichlorophenoxyl)acetyl-DL-methionine,daminozide, pyrazon, ethoxyquin, propham,S-carboxymethyl-N,N-dimethyldicarbamate, phosphan, merphos, ethephon,tricamba, amiben, glufosinate, indole-3-butyric acid, β-naphthoxyaceticacid, triclopyr, 9-undecylenic acid, oxyflurofen, dinitrocresol,flurtamone, diflufenican, difunon, fomesafen, clethodim, sethoxydim,haloxyfop, tralkoxydim, fenoxaprop, fluazifop, phaseolotoxin,rhizobitoxine, barban, ethephon, tetcyclacis, mepiquat chloride,ancymidol, uniconzaole, paclobutrazol, diquatop, pendimethalin,karbutilate, asulam, clopyralid, fluroxypyr, chlorimuron, chlorsulfuron,metsulfuron, buthidazole, imazamethabenz, imazapyr, imazaquin,imazethapry, isoxaben, cinmethylin, ethofumesate, acephate, aldicarb,aldoxycarb, aldrin, d-trans allethrin, allyxycarb, aminocarb, amitraz,azinphos, azinphos, azocyclotin, azothoate, bendiocarb, benzomate,binapacryl, bomyl, 2-sec-butylphenyl N-methylcarbamate, bromophos,bromophos-ethyl, bromopropylate, butacarb, butocarboxim, chlordane,chlordecone, heptachlor, lindane, methoxychlor, toxaphene,butoxicarboxim, carbaryl, carbofuran, carbophenothion, cartap,chloridimeform, chlorfenethol, chlorfenvinphos, chlormephos,chlorobenzilate, chloropropylate, chlorphoxim, chlorpyrifos,chlorthiophos, coumaphos, 2-chlorophenyl-N-methylcarbamate, crufomate,cryolite, cyanofenphos, cyanophos, cyhexatin, cypermethrin, cythioate,dichloro diphenyl trichloroethane, 2,2-dichlorovinyl o,o-dimethylphosphate, demeton, demeton-S-methyl, dialifor, diazinon, dicofol,dicrotophos, dieldrin, dienochlor, diflubenzuron, dimefox, dimethoate,dimethrin, dinobuton, dioxacarb, dioxathion, disulfoton,2-methyl-4,6-dinitrophenol, d-phenothrin, endosulfan, enfrin, o-ethylo(4-nitrophenyl) phenylphosphonothioate, ethyl p-nitrophenylthionobenzenephosphonate, ethiofencarb, ethion, ethoate, ethoprop,etrimfos, famphur, fenbutatin-oxide, fenitrothion, fenson,fensulfothion, fenthion, fenvalerate, fonofos, formetanatehydrochloride, formothion, fosthietan, hydroprene, isofenphos,isoxathion, isothioate, malathion, mecarbam, mecarphon, menazon, meobal,mephosfolan, mercaptodimethur, methamidophos, methidathion, methomyl,methoprene, isoprocarb, mirex, monocrotophos, m-tolyl-N-methylcarbamate,naled, nicotine, omethoate, oxamyl, oxydemeton-methyl, oxydisulfoton,parathion, permethrin, phenthoate, phorate, phosalone, phosmet,phosphamidon, phoxim, pirimicarb, pirimiphos, plifenate, profenofos,promecarb, propargite, propetamphos, propoxur, prothiophos, prothoate,quinalphos, resmethrin, ronnel, ryania, salithion, schradan, sulfotepp,sulprofos, temephos, tetraethyl diphosphate, terbufos,tetrachlorvinphos, tetradifon, tetramethrin, tetrasul,thiocyclamhydrogenoxalate, thiometon, thioquinox, triazophos,trichloronate, trichloron, vamidothion, melvinphos, trichlorofon,O,O-dimethyl phosphorochloriodothioate, methyl parathion, demeton O,dicapthon, O,O-diethylphosphorochloridothioate, propham, matacil, amixture of m 1-ethylpropyl!phenylmethylcarbamate and m1-ethylpropyl!phenylmethylcarbamate, pyrethrum, benzyl thiocyanate,rotenone, eugenol, aminozide, ancymidol, anthraquinone, brodifacoum,bromadiolone, butoxy polypropylene glycol, carbon tetrachloride,chloflurecolmethyl ester, chlormequat chloride, chlorophacinone,chloropicrin, chlorphonium, chlonitralid, coumachlor, coumafuryl,crimidine, cyoxmetril, deet, diazacosterol hydrochloride, dibutylphthalate, ethyl hexanediol, dichlofenthion, difenacoum, dikegulacsodium, diphenylamine, ethephone, fenamiphos, fluoroacetamide, glyoxime,gossyplure, heliotropin acetal, kinoprene, maleic hydrazine,metaldehyde, metam-sodium, naphthalene acetamide, 1-naphthaleneaceticacid, nitrapyrin, pyriminal, scillirosid, sesamex, sulfoxide,trifenmorph, triprene, and warfarin.
 37. The composition of claim 36wherein the intercalated phyllosilicate is exfoliated into apredominance of single platelets having said intercalant pesticidecomplexed onto said platelet surfaces.
 38. The composition of claim 36wherein the pesticide carrier comprises a water-miscible organic solventselected from the group consisting of alcohols, ketones, aldehydes,esters, glycols, glycerols, ethers, and mixtures thereof.
 39. Thecomposition of claim 36 wherein the organic liquid carrier is amonohydric alcohol having 1 to about 5 carbon atoms.
 40. The compositionof claim 36 wherein the organic liquid carrier is a polyhydric alcoholselected from the group consisting of glycols, glycerols, and mixturesthereof.
 41. The composition of claim 36 wherein the intercalatedphyllosilicate material is free of a compound having an onium ion or asilane coupling agent.
 42. The composition of claim 36 having aviscosity of at least 5000 centipoise.
 43. The composition of claim 36wherein the composition is a thixotropic gel.
 44. The composition ofclaim 4 wherein said layered material has a moisture content of about 4%to about 5000% by weight, based on the dry weight of said layeredmaterial and said water is capable of dissolving said intercalantpolymer.
 45. The composition of claim 4 wherein the moisture content ofsaid layered material is about 30% to about 40% by weight based on thedry weight of said layered material.
 46. The composition of claim 4wherein the moisture content of said layered material is about 35% toabout 40% by weight based on the dry weight of said layered material.47. The composition of claim 4 wherein the moisture content of saidlayered material is about 5% to about 50% by weight water, based on thedry weight of said layered material.
 48. The composition of claim 47wherein the moisture content of said layered material is about 7% toabout 100% by weight, based on the dry weight of said layered material.